Resins for underlayers

1. A polymeric reaction product comprising polymerized units of one or more tetraaryl monomers of formula (1) and one or more monomers chosen from formulae (2) and (3):

wherein AG represents an activating group chosen from OR, NR 2 , and SR; Ar 1 , Ar 2 , Ar 3 and Ar 4 independently represent an aryl moiety; R is independently H, an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; R 1 , R 2 , R 3 , and R 4 are independently an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; a is an integer from 0 to 4; b, c, and d are independently integers from 0 to 5; R 5 is selected from the group consisting of H, optionally substituted C 1-60 aliphatic moiety, and optionally substituted C 5-60 aryl moiety; Ar 5 is an optionally substituted C 5-60 aryl moiety, each R 6 is independently chosen from H, optionally substituted C 1-60 aliphatic moiety, and optionally substituted C 5-60 aryl moiety, and X is OH, C 1-2 alkoxy group or a halogen; wherein at least one of Ar 1 , Ar 2 , Ar 3 and Ar 4 is an aryl moiety having 2 or more fused aromatic rings, and wherein none of Ar 1 , Ar 2 , Ar 3 and Ar 4 are taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring.

2. The polymeric reaction product of claim 1 wherein AG is OR.

3. The polymeric reaction product of claim 1 wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently chosen from phenyl, biphenyl, naphthalenyl, anthracenyl, phenanthrenyl, pyrenyl, tetracenyl, triphenylenyl, tetraphenyl, benzo[f]tetraphenyl, benzo[m]tetraphenyl, benzo[k]tetraphenyl, pentacenyl, perylenyl, benzo[a]pyrenyl, benzo[e]pyrenyl, benzo[ghi]perylenyl, coronenyl, quinolonyl, 7,8-benzoquinolinyl, fluorenyl, chrysenyl, triphenylenyl, and 12H-dibenzo[b,h]fluorenyl.

4. A composition comprising the polymeric reaction product of claim 1 , an organic solvent, and optionally one or more additives chosen from curing agents and surfactants.

5. The composition of claim 4 wherein the curing agent is an acid or a thermal acid generator.

6. A method of forming a patterned layer comprising disposing a layer of the composition of claim 4 on a substrate; removing organic solvent to form a polymeric underlayer; disposing a layer of a photoresist on the polymeric underlayer; exposing the photoresist layer to actinic radiation through a mask; developing the exposed photoresist layer to form a resist pattern; and transferring the pattern to the polymeric underlayer to expose portions of the substrate.

7. A tetraaryl methane monomer having the formula (1)

wherein AG represents an activating group chosen from OR, NR 2 , and SR; Ar 1 , Ar 2 , Ar 3 and Ar 4 independently represent an aryl moiety; R is independently H, an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; R 1 , R 2 , R 3 , and R 4 are independently an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; a is an integer from 0 to 4; and b, c, and d are independently integers from 0 to 5; wherein at least one of Ar 1 , Ar 2 , Ar 3 and Ar 4 is an aryl moiety having 2 or more fused aromatic rings, and wherein none of Ar 1 , Ar 2 , Ar 3 and Ar 4 are taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring; wherein when AG is OR, R is not a H atom, and wherein when AG is NR 2 and one R is a H atom, the other R is not a C 6 aryl moiety.

8. A tetraaryl monomer having the general formula (1-2):

AG represents an activating group chosen from OR, NR2, and SR; Ar 1 , Ar 2 , Ar 3 and Ar 4 independently represent an aryl moiety; R is independently H, an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; R 1 , R 2 , R 3 , and R 4 are independently an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; any 2 of Ar 1 , Ar 2 , Ar 3 and Ar 4 may be taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring; a is an integer from 0 to 4; b is an integer from 0 to 5; and c″ and d″ are independently integers from 0 to 4; wherein when AG is NR 2 , the two groups are nor aryl moieties simultaneously.

9. A polymeric reaction product comprising polymerized units of one or more tetraaryl monomers of claim 8 and one or more monomers chosen from formulae (2) and (3):

wherein R 5 is selected from the group consisting of H, optionally substituted C 1-60 aliphatic moiety, and optionally substituted C 5-60 aryl moiety; Ar 5 is an optionally substituted C 5-60 aryl moiety; each R 6 is independently selected from the group consisting of H, optionally substituted C 1-60 aliphatic moiety, and optionally substituted C 5-60 aryl moiety; and X is OH, C 1-2 alkoxy group or a halogen.

10. A composition comprising the polymeric reaction product of claim 9 , an organic solvent, and optionally one or more additives chosen from curing agents and surfactants.

11. A method of forming a patterned layer comprising disposing a layer of the composition of claim 10 on a substrate; removing organic solvent to form a polymeric underlayer; disposing a layer of a photoresist on the polymeric underlayer; exposing the photoresist layer to actinic radiation through a mask; developing the exposed photoresist layer to form a resist pattern; and transferring the pattern to the polymeric underlayer to expose portions of the substrate.

12. A polymer comprising a repeat unit of formula (4)

wherein AG represents an activating group chosen from OR, NR 2 , and SR; Ar 1 , Ar 2 , Ar 3 and Ar 4 independently represent an aryl moiety; R is independently H, an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; R 1 , R 2 , R 3 , and R 4 are independently an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; any 2 of Ar 1 , Ar 2 , Ar 3 and Ar 4 may be taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring; a is an integer from 0 to 4; and b, c, and d are independently integers from 0 to 5; wherein at least one of Ar 1 , Ar 2 , Ar 3 and Ar 4 is an aryl moiety having 2 or more fused aromatic rings when none of Ar 1 , Ar 2 , Ar 3 and Ar 4 are joined to form a 5 or 6-membered fused alicyclic ring; A is chosen from —CH(R 5 )—, —C(R 6 ) 2 —Ar 5 —C(R 6 ) 2 —, or mixtures thereof; R 5 is selected from the group consisting of H, optionally substituted C 1-60 aliphatic moiety, and optionally substituted C 5-60 aryl moiety; Ar 5 is an optionally substituted C 5-40 aryl moiety; Ar 6 is an optionally substituted C 5-60 aryl moiety; each R 6 is independently chosen from H, optionally substituted C 1-60 aliphatic moiety, and optionally substituted C 5-60 aryl moiety; n and m each represent the number of repeat units in the polymer; n is an integer from 1 to 500; and m is an integer from 1 to 300.

13. The polymer of claim 12 wherein Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently chosen from phenyl, biphenyl, naphthalenyl, anthracenyl, phenanthrenyl, pyrenyl, tetracenyl, triphenylenyl, tetraphenyl, benzo[f]tetraphenyl, benzo[m]tetraphenyl, benzo[k]tetraphenyl, pentacenyl, perylenyl, benzo[a]pyrenyl, benzo[e]pyrenyl, benzo[ghi]perylenyl, coronenyl, quinolonyl, 7,8-benzoquinolinyl, fluorenyl, chrysenyl, triphenylenyl, and 12H-dibenzo[b,h]fluorenyl.

14. The polymer of claim 12 wherein A is —CH(R 5 )—.

15. The polymer of claim 12 wherein Ar 5 is an optionally substituted C 6-60 carbocyclic aryl moiety.

16. A composition comprising the polymer of claim 12 , an organic solvent, and optionally one or more additives chosen from curing agents and surfactants.

17. A method of forming a patterned layer comprising disposing a layer of the composition of claim 16 on a substrate; removing organic solvent to form a polymeric underlayer; disposing a layer of a photoresist on the polymeric underlayer; exposing the photoresist layer to actinic radiation through a mask; developing the exposed photoresist layer to form a resist pattern; and transferring the pattern to the polymeric underlayer to expose portions of the substrate.

18. The method of claim 17 further comprising disposing a silicon-containing layer or a hardmask layer directly on the polymeric underlayer, and disposing the photoresist layer directly on the silicon-containing layer or hardmask layer.

19. A polymeric reaction product comprising polymerized units of one or more tetraaryl monomers of formula (1)

wherein AG represents an activating group chosen from OR, NR 2 , and SR; Ar 1 , Ar 2 , Ar 3 and Ar 4 independently represent an aryl moiety; R is independently H, an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; R 1 , R 2 , R 3 , and R 4 are independently an optionally substituted C 1-30 alkyl, an optionally substituted C 2-30 alkenyl moiety, an optionally substituted C 2-30 alkynyl moiety, an optionally substituted C 7-30 aralkyl moiety, or an optionally substituted C 6-20 aryl moiety; a is an integer from 0 to 4; and b, c, and d are independently integers from 0 to 5, wherein at least one of Ar 1 , Ar 2 , Ar 3 and Ar 4 is an aryl moiety having 2 or more fused aromatic rings, and wherein none of Ar 1 , Ar 2 , Ar 3 and Ar 4 are taken together along with the carbon to which they are attached to form a 5 or 6-membered fused alicyclic ring; and formed by heating the one or more tetraaryl monomers in the presence of an acid.