Method of use of epoxy-containing cycloaliphatic acrylic polymers as orientation control layers for block copolymer thin films

A method of controlling the orientation of microphase-separated domains in specific areas of a substrate coated with a block copolymer film, comprising:

• (a) forming an orientation control layer comprising an epoxy-containing cycloaliphatic acrylic polymer over a surface of a substrate,
• (b) exposing the orientation control layer pattern-wise with actinic radiation, EUV, or electron beam, to form a pattern of exposed and unexposed regions of the orientation control layer,
• (c) heating the substrate to crosslink the orientation control layer in the exposed regions,
• (d) removing uncrosslinked orientation control layer material in the unexposed regions with a solvent to uncover the surface of the substrate in the unexposed regions,
• (e) optionally, heating the substrate having the patterned crosslinked orientation control layer to remove residual solvent,
• (f) forming a block copolymer assembly layer comprising a block copolymer that forms microphase-separated domains, on a surface of the patterned crosslinked orientation control layer opposite the substrate, and
• (g) optionally, annealing the substrate to induce pattern formation in the block copolymer layer,
• wherein lamellae form perpendicular to the plane of the substrate over the crosslinked orientation control layer, and wherein lamellae form parallel to the plane of the substrate over the uncovered surface of the substrate.

A method of controlling the orientation of microphase-separated domains and the directional alignment of the microphase-separated domains in a block copolymer film, comprising:

• (a) forming an orientation control layer comprising an epoxy-containing cycloaliphatic acrylic polymer over a surface of a substrate,
• (b) heating the substrate to crosslink the orientation control layer,
• (c) optionally, rinsing the orientation control layer with a solvent,
• (d) optionally, heating the substrate to remove residual solvent,
• (e) exposing the orientation control layer pattern-wise with actinic radiation, EUV, x-ray, or electron beam, to form a pattern of exposed and unexposed regions of the orientation control layer,
• (f) optionally, rinsing the patterned orientation control layer with a solvent,
• (g) optionally, heating the substrate having the patterned orientation control layer to remove residual solvent,
• (h) forming a block copolymer assembly layer comprising a block copolymer having at least one block that forms microphase-separated domains on a surface of the patterned orientation control layer opposite the substrate, and
• (i) annealing the substrate to induce microphase-separated domains to form a pattern in the block copolymer layer,
• wherein the microphase-separated domains are lamellae,
• and wherein when a pitch of the pattern in the patterned orientation control layer is at least 200% larger than the pitch of lamellae, the lamellae form parallel to the plane of the substrate over the exposed region of the patterned orientation control layer, and form perpendicular to the plane of the substrate on the unexposed region of patterned orientation control layer.

A method of controlling the orientation of microphase-separated domains and the directional alignment of the microphase-separated domains in a block copolymer film, comprising:

• (a) forming an orientation control layer comprising an epoxy-containing cycloaliphatic acrylic polymer over a surface of a substrate,
• (b) heating the substrate to crosslink the orientation control layer,
• (c) optionally, rinsing the orientation control layer with a solvent,
• (d) optionally, heating the substrate to remove residual solvent
• (e) exposing the orientation control layer pattern-wise with actinic radiation, EUV, x-ray, or electron beam, to form a pattern of exposed and unexposed regions of the orientation control layer,
• (f) optionally, rinsing the patterned orientation control layer with a solvent,
• (g) optionally, heating the substrate having the patterned orientation control layer to remove residual solvent,
• (h) forming a block copolymer assembly layer comprising a block copolymer having at least one block that forms microphase-separated domains on a surface of the patterned orientation control layer opposite the substrate, and
• (i) annealing the substrate to induce microphase-separated domains to form a pattern in the block copolymer layer,
• wherein the microphase-separated domains are lamellac,
• and wherein when a pitch of the pattern in the patterned orientation control layer is about the same as a pitch of the pattern in the block copolymer layer, the exposed region is wetted by one domain of the block copolymer and the unexposed region is wetted by the other domain(s) of block copolymer, and the block copolymer forms a spatial replica of the underlying patterned orientation control layer.