A self-organization material according to an embodiment includes a block copolymer and a top coat material. The block copolymer contains a first block and a second block. The second block has a surface free energy higher than that of the first block. The top coat material contains a first portion having a surface free energy higher than that of the first block and lower than that of the second block, and a second portion having a surface free energy lower than that of the first block. The first portion is one of a homopolymer miscible with both the first block and the second block, and a random copolymer having a repeating unit of the first block and a repeating unit of the second block. The second portion is one of an organic siloxane-containing polymer and a fluorine-containing polymer.

High-chi diblock copolymers are disclosed whose self-assembly properties are suitable for forming hole and bar openings for conductive interconnects in a multi-layered structure. The hole and bar openings have reduced critical dimension, improved uniformity, and improved placement error compared to the industry standard poly(styrene)-b-poly(methyl methacrylate) block copolymer (PS-b-PMMA). The BCPs comprise a poly(styrene) block, which can optionally include repeat units derived from trimethylsilyl styrene, and a second block that can be a polycarbonate block or a polyester block. Block copolymers comprising a fluorinated linking group L comprising 1-25 fluorines between the blocks can provide further improvement in uniformity of the openings.

Pattern treatment compositions comprise a block copolymer and an organic solvent. The block copolymer comprises a first block and a second block. The first block comprises a unit formed from a first monomer comprising an ethylenically unsaturated polymerizable group and a hydrogen acceptor group, wherein the hydrogen acceptor group is a nitrogen-containing group. The second block comprises a unit formed from a second monomer comprising an ethylenically unsaturated polymerizable group and a cyclic aliphatic group. Wherein: (i) the second block comprises a unit formed from a third monomer comprising an ethylenically unsaturated polymerizable group, and the second monomer and the third monomer are different; and/or (ii) the block copolymer comprises a third block comprising a unit formed from a fourth monomer comprising an ethylenically unsaturated polymerizable group, wherein the fourth monomer is different from the first monomer and the second monomer. Also provided are pattern treatment methods using the described compositions. The pattern treatment compositions and methods find particular applicability in the manufacture of semiconductor devices for providing high resolution patterns.

A method of forming a fine pattern includes forming pillar-shaped guides regularly arranged on a feature layer, forming a block copolymer layer on the feature layer around the pillar-shaped guides, phase separating the block copolymer layer, forming first domains regularly arranged on the feature layer with the pillar-shaped guides, forming a second domain on the feature layer surrounding the pillar-shaped guides and the first domains, removing the first domains, and forming holes corresponding with the first domains in the feature layer by etching the feature layer using the pillar-shaped guides and the second domain as etch masks. The block copolymer layer includes a polymer blend having first and second polymer blocks having first and second repeat units, respectively, a first homopolymer and a second homopolymer. The first domains include the first polymer block and the first homopolymer, and the second domain includes the second polymer block and the second homopolymer.

According to one embodiment, a pattern forming method includes forming a resist pattern on an under-layer, forming a recessed portion in the under-layer by etching the under-layer using the resist pattern as a mask, slimming the resist pattern, forming a neutral layer having an affinity for first and second polymers on a region of the under-layer not covered with the slimmed resist pattern, forming a block copolymer film containing the first polymer and the second polymer on the slimmed resist pattern and the neutral layer, and forming a microphase separation pattern comprising a first portion formed of the first polymer and a second portion formed of the second polymer by applying microphase separation processing to the block copolymer film.

A pattern forming method includes forming a guide pattern on a substrate including first and second regions and applying a directed self-assembly material including a first and a second polymer portion to the substrate. The first region is irradiated with an energy beam. The substrate is subjected to a heating process after irradiation and the directed self-assembly material in the second region separates into a first polymer phase and a second polymer phase. The directed self-assembly material is removed from the first region after irradiation.

Pattern treatment compositions comprise a block copolymer and an organic solvent. The block copolymer comprises a first block and a second block. The first block comprises a unit formed from a first monomer comprising an ethylenically unsaturated polymerizable group and a hydrogen acceptor group, wherein the hydrogen acceptor group is a nitrogen-containing group. The second block comprises a unit formed from a second monomer comprising an ethylenically unsaturated polymerizable group and an aromatic group, provided that the second monomer is not styrene. Wherein: (i) the second block comprises a unit formed from a third monomer comprising an ethylenically unsaturated polymerizable group, and the second monomer and the third monomer are different; and/or (ii) the block copolymer comprises a third block comprising a unit formed from a fourth monomer comprising an ethylenically unsaturated polymerizable group. Also provided are pattern treatment methods using the described compositions. The pattern treatment compositions and methods find particular applicability in the manufacture of semiconductor devices for providing high resolution patterns.

A method of fabricating a semiconductor device is disclosed. The method includes forming a first patterned hard mask over a material layer. The first patterned hard mask defines an opening. The method also includes forming a direct-self-assembly (DSA) layer having a first portion and a second portion within the opening, removing the first portion of the DSA layer, forming spacers along sidewalls of the second portion of the DSA layer and removing the second portion of the DSA layer. The spacers form a second patterned hard mask over the material layer.

Pattern treatment methods comprise: (a) providing a semiconductor substrate comprising a patterned feature on a surface thereof; (b) applying a pattern treatment composition to the patterned feature, wherein the pattern treatment composition comprises a block copolymer and a solvent, wherein the block copolymer comprises a first block and a second block, wherein the first block comprises a unit formed from a first monomer comprising an ethylenically unsaturated polymerizable group and a hydrogen acceptor group, wherein the hydrogen acceptor group is a nitrogen-containing group, and the second block comprises a unit formed from a second monomer comprising an ethylenically unsaturated polymerizable group and a cyclic aliphatic group; and (c) rinsing residual pattern treatment composition from the substrate, leaving a portion of the block copolymer bonded to the patterned feature. The methods find particular applicability in the manufacture of semiconductor devices for providing high resolution patterns.

Pattern treatment methods comprise: (a) providing a semiconductor substrate comprising a patterned feature on a surface thereof; (b) applying a pattern treatment composition to the patterned feature, wherein the pattern treatment composition comprises a block copolymer and a solvent, wherein the block copolymer comprises a first block and a second block, wherein the first block comprises a unit formed from a first monomer comprising an ethylenically unsaturated polymerizable group and a hydrogen acceptor group, wherein the hydrogen acceptor group is a nitrogen-containing group, and the second block comprises a unit formed from a second monomer comprising an ethylenically unsaturated polymerizable group and an aromatic group, provided that the second monomer is not styrene; and (c) rinsing residual pattern treatment composition from the substrate, leaving a portion of the block copolymer bonded to the patterned feature. The methods find particular applicability in the manufacture of semiconductor devices for providing high resolution patterns.