Hardmask surface treatment
View Patent ↗Compositions suitable for forming oxymetal hardmask layers are provided. Methods of forming oxymetal hardmask layers using such compositions are also provided, where the surface of the oxymetal hardmask layer formed has a water contact angle substantially matched to that of subsequently applied organic coatings.
1. A hardmask composition comprising: an organo-metal compound; a surface treating polymer having a surface energy of 20 to 40 erg/cm 2 and comprising as polymerized units one or more monomers comprising a surface treating moiety chosen from hydroxyl, protected hydroxyl, protected carboxyl, and mixtures thereof; and a solvent; wherein the organo-metal compound is polymeric.
2. A hardmask composition comprising: an organo-metal compound; a surface treating polymer having a surface energy of 20 to 40 erg/cm 2 and comprising as polymerized units one or more monomers comprising a surface treating moiety chosen from hydroxyl, protected hydroxyl, protected carboxyl, and mixtures thereof; and a solvent; wherein the organo-metal compound is chosen from:
(i) oligomer comprising Group 3 to Group 14 metal-containing pendant groups;
(ii) compounds of formula (2)
where R 1 =H or CH 3 ; M=a Group 3 to Group 14 metal; L is a ligand; and n refers to the number of ligands and is an integer from 1-4;
(iii) compounds of formula (3)
where R 2 =(C 1 -C 6 )alkyl; M 1 is a Group 3 to Group 14 metal; R 3 =(C 2 -C 6 )alkylene-X— or (C 2 -C 6 )alkylidene-X—; each X is independently chosen from O and S; z is an integer from 1-5; L 1 is a ligand; m refers to the number of ligands and is an integer from 1-4; and p=an integer from 2 to 25; and
(iv) mixtures thereof.
3. The composition of claim 1 wherein the surface treating polymer comprises a protected carboxyl group.
4. The composition of claim 3 wherein the protected carboxyl comprises an ester having a quaternary carbon bonded directly to the alkoxy oxygen of the ester group.
5. The composition of claim 1 wherein the surface treating polymer is present in an amount of 0.5 to 50 wt %, based on the weight of the composition.
6. The composition of claim 1 wherein the organo-metal compound comprises a Group 3 to Group 14 metal.
7. A method of forming a metal hardmask layer comprising: providing a substrate; coating a film of the composition of claim 1 on a surface of the substrate; and curing the film to form a metal hardmask layer.
8. The method of claim 7 wherein the cured hardmask has a water contact angle of 55 to 70°.
9. The method of claim 7 free of a separate step of contacting the metal hardmask layer with a surface treating agent.
10. A method of forming a patterned oxymetal hardmask comprising: providing a substrate; coating a film of a composition comprising a polymeric organo-metal compound; a surface treating agent having a surface energy of 20 to 40 erg/cm 2 and comprising as polymerized units one or more monomers comprising a surface treating moiety chosen from protected hydroxyl, protected carboxyl, and mixtures thereof, and a solvent on a surface of the substrate; causing the surface treating agent to migrate to the surface of the film; and curing the film to form an oxymetal hardmask layer having a patterned surface comprising regions of different surface energies.
11. The composition of claim 1 wherein the surface treating polymer comprises pendant groups comprising the surface treating moiety.
12. The composition of claim 1 wherein the surface treating polymer comprises ethylenically unsaturated monomers as polymerized units.
13. The composition of claim 1 wherein the one or more monomers comprising a surface treating moiety are chosen from hydroxystyrenes, (meth)acrylate esters, and silsesquioxanes.
14. The composition of claim 1 wherein the surface treating moiety is chosen from protected hydroxyl, protected carboxyl, and mixtures thereof.
15. The composition of claim 1 wherein the protected hydroxyl is chosen from methoxymethyl ethers, tetrhydropyranyl ethers, tert-butyl ethers, allyl ethers, benzyl ethers, tert-butyldimethylsilyl ethers, tert-butyldiphenylsilyl ethers, acetonides, benzylidene acetals, pivalic acid esters, benzoic acid esters, and tert-butylcarbonate.
16. The composition of claim 1 wherein the surface treating polymer comprises as polymerized units one or more monomers chosen from (meth)acrylate esters, styrene monomers, and hydroxystyrene monomers.