Aromatic resins for underlayers
Polymeric reaction products of certain aromatic alcohols with certain aromatic aldehydes are useful as underlayers in semiconductor manufacturing processes.
1. A reaction product formed from a combination comprising one or more first monomers of the formula
wherein Y is selected from H, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 7 -C 30 aralkyl, C 6 -C 30 aryl, substituted C 6 -C 30 aryl, —C 1 -C 30 alkylene-OR 1 , and —C 1 -C 30 alkylidene-OR 1 ; each R is independently selected from C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 7 -C 30 aralkyl, C 6 -C 30 aryl, substituted C 6 -C 30 aryl, —OR 1 , —C 1 -C 30 alkylene-OR 1 , and —C 1 -C 30 alkylidene-OR 1 ; R 1 is selected from H, C 1 -C 30 alkyl, C 6 -C 30 aryl, substituted C 6 -C 30 aryl, and C 7 -C 30 aralkyl; and n is an integer selected from 0 to 7; and one or more second monomers of formula (IIa) or (IIb)
wherein A represents 1 to 4 fused aromatic rings; A1 represents 1 to 3 fused aromatic rings; each of A2 and A3 may be present or absent and each of A2 and A3 represents 1 to 2 fused aromatic rings; each R 2 is independently selected from C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 7 -C 30 aralkyl, C 6 -C 30 aryl, substituted C 6 -C 30 aryl, —OR 3 , —C 1 -C 30 alkylene-OR 3 ; each R 3 is selected from H, C 1 -C 30 alkyl, and C 6 -C 30 aryl; and m is an integer from 0 to 13; wherein A1, A2 and A3 represent a total of 3 fused aromatic rings.
2. The reaction product of claim 1 wherein n=0 to 4.
3. The reaction product of claim 1 wherein each R is independently selected from C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 7 -C 30 aralkyl, C 6 -C 30 aryl, substituted —C 6 -C 30 aryl, —OR 1 , —C 1 -C 12 alkylene-OR 1 , and —C 1 -C 20 alkylidene-OR 1 .
4. The reaction product of claim 1 wherein each R is independently selected from hydroxyl, methyl, ethyl, propyl, iso-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclopentenylmethyl, cyclohexenylmethyl, 2-cyclohexenylmeth-1-yl, methoxy, ethoxy, propyloxy, phenyl, tolyl, xylyl, naphthyl, biphenyl, benzyl, phenethyl, naphthylmethyl, pyerenylmethyl, antracenylmethyl, methoxy, ethoxy, propyloxy, phenyloxy, naphthyloxy, benzyloxy, phenethyloxy, methoxymethyl, methoxyethyl, methoxyphenyl, and methoxynaphthyl.
5. The reaction product of claim 1 wherein second monomer is substituted with one or more hydroxyls.
6. A process for preparing a reaction product comprising reacting one or more first monomers of the formula
wherein Y is selected from H, C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 7 -C 30 aralkyl, C 6 -C 30 aryl, substituted C 6 -C 30 aryl, —C 1 -C 30 alkylene-OR 1 , and —C 1 -C 30 alkylidene-OR 1 ; each R is independently selected from C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 7 -C 30 aralkyl, C 6 -C 30 aryl, substituted C 6 -C 30 aryl, —OR 1 , —C 1 -C 30 alkylene-OR 1 , and —C 1 -C 30 alkylidene-OR 1 ; R 1 is selected from H, C 1 -C 30 alkyl, C 6 -C 30 aryl, substituted C 6 -C 30 aryl, and C 7 -C 30 aralkyl; and n is an integer selected from 0 to 7; with one or more second monomers of formula (IIa) or (IIb)
wherein A represents 1 to 4 fused aromatic rings; A1 represents 1 to 3 fused aromatic rings; each of A2 and A3 may be present or absent and each of A2 and A3 represents 1 to 2 fused aromatic rings; each R 2 is independently selected from C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 7 -C 30 aralkyl, C 6 -C 30 aryl, substituted C 6 -C 30 aryl, —OR 3 , —C 1 -C 30 alkylene-OR 3 ; each R 3 is selected from H, C 1 -C 30 alkyl, and C 6 -C 30 aryl; and m is an integer from 0 to 13; wherein A1, A2 and A3 represent a total of 3 fused aromatic rings in the presence of an acid, and optionally in a solvent.
7. The process of claim 6 wherein the solvent is polar.
8. The process of claim 6 wherein the acid is selected from dicarboxylic acids, mineral acids and sulfonic acids.
9. A polymeric reaction product produced by the process of claim 6 .
10. A composition comprising the reaction product of claim 1 , organic solvent, and optionally one or more additives chosen from curing agents, crosslinking agents, and surfactants.
11. A process of forming a patterned layer comprising disposing a layer of the composition of claim 10 on a substrate; removing organic solvent to form a reaction product layer; disposing a layer of a photoresist on the reaction product layer; 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 reaction product layer to expose portions of the substrate.
12. The process of claim 11 further comprising the steps of patterning the substrate; and then removing the patterned reaction product layer.
13. The process of claim 11 further comprising the steps of disposing a conformal silicon-containing layer over the patterned reaction product layer and exposed portions of the substrate; partially etching the silicon-containing layer to expose a top surface of the patterned polymeric reaction product layer and a portion of the substrate.