Undercoat agent and method of forming pattern of layer containing block copolymer

Patent metadata

Field	Value
Publication number	US-9834696-B2
Application number	US-201615156170-A
Country	US
Kind code	B2
Filing date	May 16, 2016
Priority date	Mar 14, 2012
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

An undercoat agent including a block copolymer having a plurality of blocks bonded formed on a substrate. The undercoat agent contains a resin component that includes a structural unit having an aromatic ring and a structural unit having no aromatic ring, and the resin component includes a group which can interact with the substrate and does not include a 3 to 7-membered, ether-containing cyclic group; and a method of forming a pattern of a layer containing a block copolymer. The method includes applying an undercoat agent to a substrate to form a layer containing the undercoat agent; forming a layer containing a block copolymer having multiple blocks bonded on a surface of the layer containing the undercoat agent, followed by a phase separation of the layer containing the block copolymer; and selectively removing a phase containing at least one block of multiple blocks constituting the block copolymer.

First claim

What is claimed is:

1. A method of forming a pattern of a layer containing a block copolymer, the method comprising:
applying an undercoat agent to a substrate to form a layer comprising the undercoat agent;
forming a layer containing a block copolymer having a plurality of blocks bonded on a surface of the layer comprising the undercoat agent which has not been subjected to exposure with radiation, followed by a phase separation of the layer containing the block copolymer; and
selectively removing a phase comprising at least one block of the plurality of blocks constituting the block copolymer, wherein
the undercoat agent comprises a resin component, the resin component includes a structural unit having an aromatic ring and a structural unit having no aromatic ring,
the resin component includes a group which can interact with the substrate and does not include a 3 to 7-membered, ether-containing cyclic group,
the structural unit having an aromatic ring is at least one structural unit selected from structural units represented by general formulas (a1-1) to (a1-4) shown below;

wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; X c and X d each independently represents a hydrogen atom, a hydroxy group, a cyano group or an organic group; R c and R d each independently represents a halogen atom, —COOX e (X e represents a hydrogen atom or an organic group), an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; px represents an integer of 0 to 3, qx represents an integer of 0 to 5, and px+qx=1 to 5, provided that, when qx is an integer of 2 or more, the plurality of R c groups may be the same or different from each other; x represents an integer of 0 to 3, y represents an integer of 0 to 3, y′ represents an integer of 0 to 2, z represents an integer of 0 to 4, and in the formula (a1-2), x+y+z=1 to 7, and in the formula (a1-3), x+y+y′+z=1 to 7, provided that, when y+z or y+y′+z is an integer of 2 or more, the plurality of R d groups may be the same or different from each other; and X Ar represents a monovalent organic group containing an aromatic ring, and
the structural unit having no aromatic ring is at least one structural unit represented by any one of the formulas shown below:

wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms.

2. The method of forming a pattern of a layer containing a block copolymer according to claim 1 , wherein the amount of the structural unit having an aromatic ring, based on the combined total of all structural units constituting the resin component is 10 to 95 mol %.

3. The method of forming a pattern of a layer containing a block copolymer according to claim 1 , wherein the undercoat agent further comprises an acidic compound component or an acid generator component that generates acid upon heating or exposure.

4. The method of forming a pattern of a layer containing a block copolymer according to claim 1 , wherein the structural unit having an aromatic ring is at least one structural unit represented by general formula (a1-1) or (a1-2) shown below:

wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; X c and X d each independently represents a hydrogen atom, a hydroxy group, a cyano group or an organic group; R c and R d each independently represents a halogen atom, —COOX e (X e represents a hydrogen atom or an organic group), an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; px represents an integer of 0 to 3, qx represents an integer of 0 to 5, and px+qx=1 to 5, provided that, when qx is an integer of 2 or more, the plurality of R c groups may be the same or different from each other; x represents an integer of 0 to 3, y represents an integer of 0 to 3, z represents an integer of 0 to 4, and x+y+z=1 to 7, provided that, when y+z is an integer of 2 or more, the plurality of R d groups may be the same or different from each other.

5. The method of forming a pattern of a layer containing a block copolymer according to claim 1 , wherein the amount of the structural unit having no aromatic ring, based on the combined total of all structural units constituting the resin component is preferably 5 to 90 mol %.

6. The method of forming a pattern of a layer containing a block copolymer according to claim 1 , wherein the structural unit having an aromatic ring is at least one structural unit represented by any one of general formulas shown below;

wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, and
the structural unit having no aromatic ring is at least one structural unit represented by any one of the formulas shown below;

wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms.

7. The method of forming a pattern of a layer containing a block copolymer according to claim 1 , wherein the block copolymer is at least one block copolymer selected from the group consisting of a polystyrene-polymethyl methacrylate (PS-PMMA) block copolymer, a polystyrene-polyethyl methacrylate block copolymer, a polystyrene-(poly-t-butyl methacrylate) block copolymer, a polystyrene-polymethacrylic acid block copolymer, a polystyrene-polymethyl acrylate block copolymer, a polystyrene-polyethyl acrylate block copolymer, a polystyrene-(poly-t-butyl acrylate) block copolymer and a polystyrene-polyacrylic acid block copolymer.

Assignees

• Tokyo Ohka Kogyo Co Ltd

Inventors

• Senzaki Takahiro
• Miyagi Ken
• Kurosawa Tsuyoshi
• Shiono Daiju
• Matsumiya Tasuku
• Miyashita Kenichiro
• Ohmori Katsumi

Classifications

• C09D135/06

  Copolymers with vinyl aromatic monomers · CPC title

• C09D143/04 Primary

  Homopolymers or copolymers of monomers containing silicon · CPC title

• C09D133/08

  Homopolymers or copolymers of acrylic acid esters · CPC title

• C09D133/02 Primary

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• C09J133/06

  of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical · CPC title