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

Abstract

An undercoat agent which is used for phase separating a layer including a block copolymer having a plurality of blocks bonded formed on a substrate, wherein the undercoat agent contains a resin component, the resin component 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, including: a step (1) in which the undercoat agent is applied to a substrate to form a layer containing the undercoat agent; a step (2) in which a layer containing a block copolymer having a plurality of blocks bonded is formed on a surface of the layer containing the undercoat agent, followed by a phase separation of the layer containing the block copolymer; and a step (3) in which a phase containing at least one block of the plurality of blocks constituting the block copolymer is selectively removed.

1 . An undercoat agent which is used for phase separating a layer including a block copolymer having a plurality of blocks bonded formed on a substrate, 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, 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.   
     
     
         2 . The undercoat agent according to  claim 1 , wherein an 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 undercoat agent according to  claim 1 , wherein the group which can interact with the substrate is a carboxy group, a cyano group, an amino group or a trimethoxysilyl group. 
     
     
         4 . The undercoat agent according to  claim 1 , wherein the structural unit having an aromatic ring is a structural unit derived from a compound selected from the group consisting of an aromatic compound which contains a vinyl group and has 6 to 18 carbon atoms, an aromatic compound which contains a (meth)acryloyl group and has 6 to 18 carbon atoms and a phenolic compound which is a component of a novolac resin. 
     
     
         5 . The undercoat agent according to  claim 1 , further comprising an acidic compound component or an acid generator component that generates acid upon heating or exposure. 
     
     
         6 . A method of forming a pattern of a layer containing a block copolymer, comprising:
 applying the undercoat agent of  claim 1  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, 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.   
     
     
         7 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , wherein an 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 %. 
     
     
         8 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , wherein the group which can interact with the substrate is a carboxy group, a cyano group, an amino group or a trimethoxysilyl group. 
     
     
         9 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , wherein the structural unit having an aromatic ring is a structural unit derived from a compound selected from the group consisting of an aromatic compound which contains a vinyl group and has 6 to 18 carbon atoms, an aromatic compound which contains a (meth)acryloyl group and has 6 to 18 carbon atoms and a phenolic compound which is a component of a novolac resin. 
     
     
         10 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , further comprising an acidic compound component or an acid generator component that generates acid upon heating or exposure. 
     
     
         11 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , wherein 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. 
       
     
     
         12 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , wherein the structural unit having no aromatic ring is at least one structural unit selected from structural units represented by general formulas (a2-1) and (a2-2) 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 a  and X b  each independently represents a hydrogen atom or an organic group which does not contain an aromatic ring; and le represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms. 
       
     
     
         13 . The method of forming a pattern of a layer containing a block copolymer according to  claim 8 , wherein the structural unit having no aromatic ring comprises the group which can interact with the substrate. 
     
     
         14 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , wherein the structural unit having no aromatic ring is at least one structural unit represented by any one of formulas (a21-1) and (a21-2) 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; R b  represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms; Y 01  represents a single bond or a divalent linking group which does not contain an aromatic ring; X 01  represents a hydrogen atom, a carboxyl group, a cyano group, an amino group, a trialkoxysilyl group, a lactone-containing cyclic group or an organic group containing a fluorine atom, provided that, when X 01  is a hydrogen atom, Y 01  represents a single bond, and when X 01  is a carboxy group, a cyano group, an amino group or a trialkoxysilyl group, Y 01  represents a divalent linking group which does not have an aromatic ring; Y 02  represents a divalent linking group which does not have an aromatic ring; and X 02  represents a carboxy group, a cyano group, an amino group or a trialkoxysilyl group. 
       
     
     
         15 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , wherein
 the structural unit having no aromatic ring is at least one structural unit represented by any one of 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. 
       
     
     
         16 . The method of forming a pattern of a layer containing a block copolymer according to  claim 15 , 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 e  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. 
       
     
     
         17 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , 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 %. 
     
     
         18 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , 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 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. 
     
     
         19 . The method of forming a pattern of a layer containing a block copolymer according to  claim 6 , 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.