Pattern formation methods
Methods of forming an electronic device, comprise: (a) providing a semiconductor substrate comprising one or more layers to be patterned; (b) forming a photoresist layer over the one or more layers to be patterned, wherein the photoresist layer is formed from a composition that comprises: a matrix polymer comprising a unit having an acid labile group; a photoacid generator; and an organic solvent; (c) coating a photoresist overcoat composition over the photoresist layer, wherein the overcoat composition comprises: a matrix polymer; an additive polymer; a basic quencher; and an organic solvent; wherein the additive polymer has a lower surface energy than a surface energy of the matrix polymer, and wherein the additive polymer is present in the overcoat composition in an amount of from 1 to 20 wt % based on total solids of the overcoat composition; (d) exposing the photoresist layer to activating radiation; (e) heating the substrate in a post-exposure bake process; and (f) developing the exposed film with an organic solvent developer. The methods have particular applicability in the semiconductor manufacturing industry.
1. A pattern formation method, comprising:
(a) providing a semiconductor substrate comprising one or more layers to be patterned;
(b) forming a photoresist layer over the one or more layers to be patterned, wherein the photoresist layer is formed from a composition that comprises: a matrix polymer comprising a unit having an acid labile group; a photoacid generator; and an organic solvent;
(c) coating a photoresist overcoat composition over the photoresist layer, wherein the overcoat composition comprises: a matrix polymer; an additive polymer; a basic quencher; and an organic solvent; wherein the matrix polymer is free of fluorine and silicon and the additive polymer comprises a unit containing a fluorine atom, wherein the additive polymer has a lower surface energy than a surface energy of the matrix polymer, and wherein the additive polymer is present in the overcoat composition in an amount of from 1 to 20 wt % based on total solids of the overcoat composition;
(d) exposing the photoresist layer to activating radiation;
(e) heating the substrate in a post-exposure bake process; and
(f) developing the exposed photoresist layer with an organic solvent developer.
2. The method of claim 1 , wherein the additive polymer comprises a unit containing a fluoroalcohol.
3. The method of claim 1 , wherein the matrix polymer comprises a unit formed from a monomer of the following general formula (I):
wherein: R 1 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 2 is chosen from optionally substituted C1 to C15 alkyl; X 1 is oxygen, sulfur or is represented by the formula NR 3 , wherein R 3 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and Z 1 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —COO— and —CONR 4 — wherein R 4 is chosen from hydrogen and optionally substituted C1 to C10 alkyl.
4. The method of claim 1 , wherein the additive polymer is formed from a monomer having the following general formula (II);
wherein: R 10 is chosen from hydrogen and optionally substituted C1 to C3 alkyl; R 11 is chosen from optionally substituted C1 to C15 alkyl; X 2 is oxygen, sulfur or is represented by the formula NR 12 , wherein R 12 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and Z 3 is a single bond or a spacer unit chosen from optionally substituted aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from —O—, —S—, —NHSO 2 —, —COO— and —CONR 13 — wherein R 13 is chosen from hydrogen and optionally substituted C1 to C10 alkyl; and wherein the monomer of general formula (II) contains a fluorine atom.
5. The method of claim 1 , wherein the basic quencher comprises a basic moiety on the matrix polymer.
6. The method of claim 1 , wherein the basic quencher comprises an additive separate from the matrix polymer.
7. The method of claim 1 , wherein the additive polymer is present in the overcoat composition in an amount of from 3 to 15 wt % based on total solids of the overcoat composition.
8. The method of claim 1 , wherein the photoresist layer is exposed to the activating radiation in an immersion lithography process.
9. The method of claim 1 , wherein the additive polymer comprises a unit formed from a monomer comprising a polymerizable group chosen from (alkyl)acrylate, (alkyl)acrylamide, allyl, maleimide styrene, vinyl and polycyclic groups.
10. The method of claim 9 , wherein the polymerizable group is a vinyl group.
11. The method of claim 10 , wherein the polymerizable group is an (alkyl)acrylate group.