Polymers based on cinnamic acid as a bottom antireflective coating for 157 NM photolithography

1. A bottom antireflective coating for photolithography using wavelengths of 157 nm or less, the coating being formed from a polymer comprising cinnamic acid derivatives of at least one of the following formulas I-III:

wherein:

R1 comprises at least one of H, halogen, and a straight or branched alkyl chain including 1-10 carbon atoms;

R2 for the compounds of formulas (I) and (II) comprises one or more substituents at one or more of the 1, 2, 3, 4 and 5 positions on the phenyl ring, the one or more substituents being independent of each other and each substituent comprising at least one of H, a straight or branched alkyl chain including 1-4 carbon atoms, a halogen, NO 2 , NH 2 and OH;

R2 for the compound of formula (III) comprises one or more substituents at one or more of the 1, 2, 3, 4 and 5 positions on the phenyl ring, the one or more substituents being independent of each other and each substituent comprising at least one of a straight or branched alkyl chain including 2-4 carbon atoms, a halogen, NO 2 , NH 2 and OH;

R3 comprises

m is an integer of 1-10,000;

n is an integer of 1-10,000;

o is an integer of 1-10;

R4 comprises a carboxyl protective group, a straight or branched alkyl group including 1-4 carbon atoms, or a group cleavable by a nucleophilic reagent or acid; and

X comprises a reactive anchor group selected from the group consisting of acid anhydride, epoxide and ketene when R2 includes at least one of a straight or branched alkyl chain including 1-4 carbon atoms, Cl, Br, I, NO 2 , NH 2 and OH, and X comprises a reactive anchor group selected from the group consisting of epoxide and ketene when R2 includes at least one of H, a straight or branched alkyl chain including 1-4 carbon atoms, F, Cl, Br, I, NO 2 , NH 2 and OH;

wherein no cinnamic derivative of the crosslinkable polymer has any of the following formulas:

2. The bottom antireflective coating of claim 1 , wherein the polymer comprises at least one cinnamic acid derivative of formula (II), and the reactive anchor group is an acid anhydride group.

3. The bottom antireflective coating of claim 2 , wherein the acid anhydride group is derived from maleic anhydride, itaconic anhydride, methacrylic anhydride, cyclohexenedicarboxylic anhydride or norbornenedicarboxylic anhydride.

4. The bottom antireflective coating of claim 3 , wherein the acid anhydride group is derived from maleic anhydride.

5. The bottom antireflective coating of claim 4 , wherein the polymer has a structure according to the following formula V:

wherein R1, R2, R4, m and n are as described above for formulas (I-II).

6. The bottom antireflective coating of claim 5 , wherein the polymer has a structure of the following formula VI:

wherein R1, R2, m and n are as defined for formulas (I-Il).

7. The bottom antireflective coating of claim 1 , wherein a molar proportion of the second repeating unit X of the polymer of formula (II) is in a range from 10 to 50 mol %.

8. The bottom antireflective coating of claim 1 , wherein the polymer is crosslinked.

9. The bottom antireflective coating of claim 8 , wherein the crosslinking is achieved photochemically.

10. The bottom antireflective coating of claim 8 , wherein the crosslinking is achieved utilizing a wet chemical method.

11. The bottom antireflective coating of claim 10 , wherein the crosslinking is achieved using bifunctional amines, bifunctional alcohols or bifunctional isocyanates.

12. The bottom antireflective coating of claim 1 , wherein cinnamic acid derivatives are contained either in the polymer backbone or in side chains of the polymer.

13. A formulation for the production of a bottom antireflective coating for photolithography using wavelengths of not more than 157 nm, comprising a polymer, a solvent and a stabilizer wherein the polymer comprises cinnamic acid derivatives of at least one of the following formulas I-III:

wherein:

R 1 comprises at least one of H, halogen, and a straight or branched alkyl chain including 1-10 carbon atoms;

R 2 for the compounds of formulas (I) and (II) comprises one or more substituents at one or more of the 1, 2, 3, 4 and 5 positions on the phenyl ring, the one or more substituents being independent of each other and each substituent comprising at least one of H, a straight or branched alkyl chain including 1-4 carbon atoms, a halogen, NO 2 , NH 2 and OH;

R 2 for the compound of formula (III) comprises one or more substituents at one or more of the 1, 2, 3, 4 and 5 positions on the phenyl ring, the one or more substituents being independent of each other and each substituent comprising at least one of a straight or branched alkyl chain including 2-4 carbon atoms, a halogen, NO 2 , NH 2 and OH;

R 3 comprises

m is an integer of 1-10,000;

n is an integer of 1-10,000;

o is an integer of 1-10;

R 4 comprises a carboxyl protective group, a straight or branched alkyl group including 1-4 carbon atoms, or a group cleavable by a nucleophilic reagent or acid; and

X comprises a reactive anchor group selected from the group consisting of acid anhydride, epoxide and ketene when R 2 includes at least one of a straight or branched alkyl chain including 1-4 carbon atoms, Cl, Br, I, NO 2 , NH2 and OH, and X comprises a reactive anchor group selected from the group consisting of epoxide and ketene when R 2 includes at least one of H, a straight or branched alkyl chain including 1-4 carbon atoms, F, Cl, Br, I, NO 2 , NH 2 and OH;

wherein no cinnamic derivative of the crosslinkable polymer has any of the following formulas:

14. The formulation of claim 13 , comprising a protected, bifunctional crosslinking agent.

15. The formulation of claim 14 , wherein the protected, bifunctional crosslinking agent is selected from the group consisting of thermally labile bisamines and bifunctional thermo acids.

16. A process for the production of a bottom antireflective coating, comprising the following steps:

applying the formulation of claim 13 to a substrate by spin coating;

evaporating the solvent in a post apply bake (PAB) step; and

crosslinking the polymer contained in the formulation.

17. A process for conducting photolithography using wavelengths of 157 nm or less, comprising the step of using a polymer for the production of a bottom antireflective coating for the photolithography process, wherein the polymer comprises cinnamic acid derivatives of at least one of the following formulas I-III:

wherein:

R 1 comprises at least one of H, halogen, and a straight or branched alkyl chain including 1-10 carbon atoms;

R 2 for the compounds of formulas (I) and (II) comprises one or more substituents at one or more of the 1, 2, 3, 4 and 5 positions on the phenyl ring, the one or more substituents being independent of each other and each substituent comprising at least one of H, a straight or branched alkyl chain including 1-4 carbon atoms, a halogen, NO 2 , NH 2 and OH;

R 2 for the compound of formula (III) comprises one or more substituents at one or more of the 1, 2, 3, 4 and 5 positions on the phenyl ring, the one or more substituents being independent of each other and each substituent comprising at least one of a straight or branched alkyl chain including 2-4 carbon atoms, a halogen, NO 2 , NH 2 and OH;

R 3 comprises

m is an integer of 1-10,000;

n is an integer of 1-10,000;

o is an integer of 1-10;

R 4 comprises a carboxyl protective group, a straight or branched alkyl group including 1-4 carbon atoms, or a group cleavable by a nucleophilic reagent or acid; and

X comprises a reactive anchor group selected from the group consisting of acid anhydride, epoxide and ketene when R 2 includes at least one of a straight or branched alkyl chain including 1-4 carbon atoms, Cl, Br, I, NO 2 , NH 2 and OH, and X comprises a reactive anchor group selected from the group consisting of epoxide and ketene when R 2 includes at least one of H, a straight or branched alkyl chain including 1-4 carbon atoms, F, Cl, Br, I, NO 2 , NH 2 and OH;

wherein no cinnamic derivative of the crosslinkable polymer has any of the following formulas:

18. A composition comprising a crosslinkable polymer including cinnamic acid derivatives of at least one of the following formulas I-III:

wherein:

R1 comprises at least one of H, halogen, and a straight or branched alkyl chain including 1-10 carbon atoms;

R2 for the compounds of formulas (I) and (II) comprises one or more substituents at one or more of the 1, 2, 3, 4 and 5 positions on the phenyl ring, the one or more substituents being independent of each other and each substituent comprising at least one of H, a straight or branched alkyl chain including 1-4 carbon atoms, a halogen, NO 2 , NH 2 and OH;

R2 for the compound of formula (III) comprises one or more substituents at one or more of the 1, 2, 3, 4 and 5 positions on the phenyl ring, the one or more substituents being independent of each other and each substituent comprising at least one of a straight or branched alkyl chain including 2-4 carbon atoms, a halogen, NO 2 , NH 2 and OH;

R3 comprises

m is an integer of 1-10,000;

n is an integer of 1-10,000;

o is an integer of 1-10;

R4 comprises a carboxyl protective group, a straight or branched alkyl group including 1-4 carbon atoms, or a group cleavable by a nucleophilic reagent or acid;

X comprises a reactive anchor group selected from the group consisting of acid anhydride, epoxide and ketene when R2 includes at least one of a straight or branched alkyl chain including 1-4 carbon atoms, Cl, Br, I, NO 2 , NH 2 and OH, and X comprises a reactive anchor group selected from the group consisting of epoxide and ketene when R2 includes at least one of H, a straight or branched alkyl chain including 1-4 carbon atoms, F, Cl, Br, I, NO 2 , NH 2 and OH; and

wherein no cinnamic derivative of the crosslinkable polymer has any of the following formulas: