Method of producing structure containing phase-separated structure, method of forming pattern and method of forming fine pattern

摘要

A method of producing a structure containing a phase-separated structure, including: forming a layer including a neutralization film on a substrate; forming a layer containing a block copolymer on the layer including the neutralization film, the PA block and PB block being mutually bonded in the block copolymer, and the PB block including a structural unit other than a structural unit constituting the PA block; and subjecting the layer containing the block copolymer to an annealing treatment, such that, in the case where a surface free energy of the PA block, a surface free energy of the PB block and a surface free energy of the neutralization film are represented by a coordinate point A of the PA block, a coordinate point B of the PB block and a coordinate point N of the neutralization film, respectively in the plane of coordinates, the coordinate point N of the neutralization film is within the predetermined range.

主权项

1. A method of producing a structure containing a phase-separated structure, comprising:
applying an undercoat agent to a substrate, so as to form a neutralization film on the substrate; applying a block copolymer composition to the neutralization film, so as to form a block copolymer layer on the neutralization film, the block copolymer having a PA block and a PB block being mutually bonded; and annealing the block copolymer layer; and forming a phase-separated structure selected from the group consisting of a PA matrix cylindrical structure, a lamellar structure, or a PB matrix cylindrical structure, wherein a surface free energy of the PA block as represented by a coordinate point A of the PA block, a surface free energy of the PB block as represented by a coordinate point B of the PB block and a surface free energy of the neutralization film as represented by a coordinate point N of the neutralization film are determined from the following formulae:
γS=γSL+γL cos θ  (1)WSL=γS+γL−γSL  (2)WSL=γL(1+cos θ)  (3)γSL=γS+γL−4γSdγLd/(γSd+γLd)−4γSpγLp/(γSp+γLp)wherein each of said coordinate points A, B and N are in a plane of coordinates having an X-axis of square root of the dispersive component (d)0.5 and a Y-axis of square root of the polar component (p)0.5,wherein γS represents a surface tension of a solid selected from a PA block homopolymer film, a PB block homopolymer film or the neutralization film; γL represents a surface tension of a liquid disposed on a surface of the solid; γSL represents an interface tension between the solid and the liquid; θ represents a contact angle formed between tangential line drawn to a droplet of the liquid and the surface of the solid; WSL represents work of adhesion between the liquid and the solid; γSd represents a dispersive component of the surface free energy of the solid; γSp represents a polar component of the surface free energy of the solid; γLd represents a dispersive component of the surface free energy of the liquid; and γLp represents a liquid component of the surface free energy of the liquid, wherein, when the phase-separated structure is the PA matrix cylindrical structure, a coordinate point N of the neutralization film is within the range of an ellipse EA, wherein a point OA is a center of the ellipse EA and divides a line segment AB in the ratio of 3:7, the line segment AB is on a minor axis of the ellipse EA, a minor radius of the ellipse EA is 0.4 times the length of the line segment AB, and a major radius of the ellipse EA is 3 times the length of the line segment AB; wherein, when the phase-separated structure is the lamellar structure, the coordinate point N of the neutralization film is within the range of an ellipse E, wherein a point 0 is a center of the ellipse E and divides a line segment AB in the ratio of 5:5, the line segment AB is on a minor axis of the ellipse E, a minor radius of the ellipse E is 0.6 times the length of the line segment AB, and a major radius of the ellipse E is 3 times the length of the line segment AB; and wherein, when the phase-separated structure is the PB matrix cylindrical structure, the coordinate point N of the neutralization film is within the range of an ellipse EB, wherein a point OB is a center of the ellipse EB and divides a line segment AB in the ratio of 7:3, the line segment AB is on a minor axis of the ellipse EB, a minor radius of the ellipse EB is 0.4 times the length of the line segment AB, and a major radius of the ellipse EB is 3 times the length of the line segment AB.