Silicon-containing underlayers
Methods of manufacturing electronic devices employing wet-strippable underlayer compositions comprising a condensate and/or hydrolyzate of a polymer comprising as polymerized units one or more first unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to the polymer backbone, and one or more condensable silicon monomers are provided.
1. A composition comprising: (a) one or more solvents; (b) a condensate and/or hydrolyzate of (i) one or more condensed silicon-containing polymers comprising as polymerized units one or more first unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to a backbone of the polymer, the one or more first unsaturated monomers having the formula (1)
wherein L is a single bond or a divalent linking group; each R 1 is independently chosen from H, C 1-10 -alkyl, C-alkenyl, C 5-20 -aryl, and C 6-20 -aralkyl; each of R 2 and R 3 are independently chosen from H, C 1-4 alkyl, C 1-4 haloalkyl, halogen, C 5-20 -aryl, C 6-20 aralkyl, and CN; R 4 is chosen from H, C 1-10 alkyl, C 1-10 haloalkyl, halogen, C 5-20 -aryl, C 6-20 aralkyl, and C(═O)R 5 ; R 5 is chosen from OR 6 and N(R 7 ) 2 ; R 6 is chosen from H, and C 1-20 alkyl; each R 7 is independently chosen from H, C 1-20 alkyl, and C 6-20 aryl; each Y 1 is independently chosen from halogen, C 1-10 -alkoxy, C 5-10 -aryloxy, and C 1-10 -carboxy; and b is an integer from 0 to 2 and (ii) one or more condensable silicon monomers; wherein the condensate and/or hydrolyzate further comprises as polymerized units one or more second unsaturated monomers free of a condensable silicon-containing moiety, wherein at least one second unsaturated monomer has the formula
wherein Z is chosen from an acid decomposable group, a C 4-30 organic residue bound to the oxygen through a tertiary carbon, a C 4-30 organic residue comprising an acetal functional group, and a monovalent organic residue having a lactone moiety; and R 10 is independently chosen from H, C 1-4 alkyl, C 1-4 haloalkyl, halogen, and CN, and (c) one or more crosslinkers free of Si—O linkages.
2. The composition of claim 1 wherein at least one condensable silicon monomer has the formula (8)
Si(R 50 ) p (X) 4-p (8)
wherein p is an integer from 0 to 3; each R 50 is independently chosen from a C 1-30 hydrocarbyl moiety and a substituted C 1-30 hydrocarbyl moiety; and each X is independently chosen from halogen, C 1-10 alkoxy, —OH, —O—C(O)—R 50 , and (O—Si(R 51 ) 2 ) p2 —X 1 ; X 1 is independently chosen from halogen, C 1-10 alkoxy, —OH, and —O—C(O)—R 50 ; each R 51 is independently chosen from R 50 and X; and p2 is an integer from 1 to 10.
3. The composition of claim 2 wherein p=0 or 1.
4. The composition of claim 1 wherein L is a divalent linking group.
5. The composition of claim 4 wherein the divalent linking group is an organic radical having from 1 to 20 carbon atoms and optionally one or more heteroatoms.
6. The composition of claim 4 wherein the divalent linking group has the formula —C(═O)—O-L 1 - wherein L 1 is a single bond or an organic radical having from 1 to 20 carbon atoms.
7. The composition of claim 1 wherein at least one second unsaturated monomer has an acidic proton and having a pKa in water from −5 to 13.
8. The composition of claim 1 wherein the condensate and/or hydrolyzate further comprises as polymerized units one or more unsaturated monomers having a chromophore moiety.
9. The composition of claim 8 wherein the chromophore moiety is pendent from the polymer backbone.
10. A method comprising (a) coating a substrate with the composition of claim 1 to form a coating layer; (b) curing the coating layer to form a polymeric underlayer; (c) disposing a layer of a photoresist on the polymeric underlayer; (d) pattern-wise exposing the photoresist layer to form a latent image; (e) developing the latent image to form a patterned photoresist layer having a relief image therein; (f) transferring the relief image to the substrate; and (g) removing the polymeric underlayer by wet stripping.
11. The method of claim 10 wherein at least one condensable silicon monomer has the formula (8)
Si(R 50 ) p (X) 4-p (8)
wherein p is an integer from 0 to 3; each R 50 is independently chosen from a C 1-30 hydrocarbyl moiety and a substituted C 1-30 hydrocarbyl moiety; and each X is independently chosen from halogen, C 1-10 alkoxy, —OH, —O—C(O)—R 50 , and (O—Si(R 51 ) 2 ) p2 —X 1 ; X 1 is independently chosen from halogen, C 1-10 alkoxy, —OH, and —O—C(O)—R 50 ; each R 51 is independently chosen from R 50 and X; and p2 is an integer from 1 to 10.
12. The method of claim 10 wherein L is a divalent linking group having the formula —C(═O)—O-L 1 - wherein L 1 is a single bond or an organic radical having from 1 to 20 carbon atoms.
13. The method of claim 10 wherein the condensate and/or hydrolyzate further comprises as polymerized units one or more unsaturated monomers having a chromophore moiety.