Silicon-containing underlayers

1. A composition comprising: (a) one or more solvents; and (b) a condensate and/or hydrolyzate of (i) one or more organic polymers comprising as polymerized units: one or more first unsaturated monomers having a moiety having an acidic proton and a pKa in water from −5 to 13; one or more second unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to the organic polymer backbone; one or more third unsaturated monomers free of an acidic moiety having an acidic proton and having a pKa in water of −5 to 13, and free of a condensable silicon-containing moiety, wherein at least one third monomer has the formula (5)

wherein ADG is an acid decomposable group; and R 21 is H, C 1-4 -alkyl, C 1-4 -haloalkyl, halogen, or CN; and one or more unsaturated monomers having a chromophore moiety,

and (ii) one or more condensable silicon monomers.

2. The composition of claim 1 wherein at least one first unsaturated monomer has an acidic moiety selected from the group consisting of carboxylic acid, sulfonic acid, sulfinic acid, sulfamic acid, boronic acid, phosphoric acid, and combinations and acid salts thereof, a hydroxyaryl group, an unsubstituted imide group, a mercapto group, and a C 1-20 -hydroxyl-substituted haloalkyl group.

3. The composition of claim 1 wherein at least one first unsaturated monomer has the formula (1)

wherein L 1 is a single bond or a divalent linking group; AM is an acidic moiety having an acidic proton and having a pKa in water from −5 to 13; each of R 1 and R 2 is independently H, C 1-4 -alkyl, C 1-4 -haloalkyl, optionally substituted C 6-20 -aryl, halogen, or CN; R 3 is H, C 1-10 -alkyl, C 1-10 -haloalkyl, optionally substituted C 6-20 -aryl, halogen, or —C(═O)R 4 ; R 4 is OR 5 or N(R 6 ) 2 ; R 5 is H, C 1-20 -alkyl, C 5-30 -aryl, C 6-20 -aralkyl or a monovalent organic residue having a lactone moiety; and each R 6 is independently H, C 1-20 -alkyl, or C 6-20 -aryl; wherein any two of L 1 , R 1 , R 2 and R 3 may be taken together with the carbons to which they are attached to form a 5 to 7-membered ring.

4. The composition of claim 3 wherein L 1 is a single covalent bond or a divalent organic radical having from 1 to 20 carbon atoms and optionally one or more heteroatoms.

5. The composition of claim 1 wherein the condensable silicon-containing moiety has the formula (2)

*-L 2 -SiR 7 b Y 1 3-b   (2)

wherein L 2 is a single bond or a divalent linking group; each R 7 is independently H, C 1-10 -alkyl, C 2-20 -alkenyl, C 5-20 -aryl, or C 6-20 -aralkyl; each Y 1 is independently halogen, C 1-10 -alkoxy, C 5-10 -aryloxy, or C 1-10 -carboxy; b is an integer from 0 to 2; and * denotes the point of attachment to the monomer.

6. The composition of claim 1 wherein at least one second unsaturated monomer has the formula (3)

wherein L 2 is a single bond or a divalent linking group; each R 7 is independently H, C 1-10 -alkyl, C 2-20 -alkenyl, C 5-20 -aryl, or C 6-20 -aralkyl; each of R 8 and R 9 is independently H, C 1-4 -alkyl, C 1-4 -haloalkyl, halogen, C 5-20 -aryl, C 6-20 -aralkyl, or CN; R 10 is H, C 1-10 -alkyl, C 1-10 -haloalkyl, halogen, C 5-20 -aryl, C 6-20 -aralkyl, or C(═O)R 11 ; R 11 is OR 12 or N(R 13 ) 2 ; R 12 is H, C 1-20 alkyl, C 5-20 -aryl, or C 6-20 -aralkyl; each R 13 is independently H, C 1-20 -alkyl, or C 5-20 -aryl; each Y 1 is independently halogen, C 1-10 -alkoxy, C 5-10 -aryloxy, or C 1-10 -carboxy; and b is an integer from 0 to 2.

7. The composition of claim 6 wherein L 2 is a divalent organic radical having from 1 to 20 carbon atoms and optionally one or more heteroatoms.

8. The composition of claim 6 wherein the divalent linking group has the formula —C(═O)—O-L 3 - wherein L 3 is a single bond or an organic radical having from 1 to 20 carbon atoms.

9. The composition of claim 1 wherein the chromophore moiety is pendent from the organic polymer backbone.

10. The composition of claim 9 wherein the chromophore moiety is selected from the group consisting of from furyl, pyryl, thiophenyl, pyridyl, phenyl, naphthyl, acenaphthyl, fluorenyl, carbazolyl, anthracenyl, phenanthryl, pyrenyl, coronenyl, tetracenyl, pentacenyl, tetraphenyl, benzotetracenyl, triphenylenyl, perylenyl, benzyl, phenethyl, tolyl, xylyl, styrenyl, vinylnaphthyl, vinylanthracenyl, dibenzothiophenyl, thioxanthonyl, indolyl, and acridinyl.

11. The composition of claim 1 wherein at least one condensable silicon monomer has the formula (9)

Si(R 50 ) p (X) 4-p   (9)

wherein each R 50 is independently a C 1-30 hydrocarbyl moiety or a substituted C 1-30 hydrocarbyl moiety; and each X is independently halogen, C 1-10 alkoxy, —OH, —O—C(O)—R 50 , —(O—Si(R 51 ) 2 ) p2 —X 1 , or —(Si(R 51 ) 2 ) p3 —X 1 ; X 1 is independently halogen, C 1-10 alkoxy, —OH, or —O—C(O)—R 50 ; each R 51 is independently R 50 or X; p is an integer from 0 to 3; p2 is an integer from 1 to 10; and p3 is an integer from 1 to 10.

12. The composition of claim 11 wherein p=0 or 1.

13. A method comprising (a) coating a substrate with a composition to form a coating layer, wherein the composition comprises: (1) one or more solvents; and (2) a condensate and/or hydrolyzate of (i) one or more organic polymers comprising as polymerized units: one or more first unsaturated monomers having a moiety having an acidic proton and a pKa in water from −5 to 13; one or more second unsaturated monomers having a condensable silicon-containing moiety, wherein the condensable silicon-containing moiety is pendent to the organic polymer backbone; and one or more third unsaturated monomers free of an acidic moiety having an acidic proton and having a pKa in water of −5 to 13, and free of a condensable silicon-containing moiety, wherein at least one third monomer has the formula (5)

wherein ADG is an acid decomposable group; and R 21 is H, C 1-4 -alkyl, C 1-4 -haloalkyl, halogen, or CN, and (ii) one or more condensable silicon monomers; (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; (0 transferring the relief image to the substrate; and (g) removing the polymeric underlayer by wet stripping.

14. The method of claim 13 wherein the organic polymer further comprises as polymerized units one or more unsaturated monomers having a chromophore moiety.

15. The method of claim 13 wherein the polymeric underlayer is removed by wet stripping at room temperature.