Pattern-forming method, and composition

Abstract

A pattern-forming method includes: forming a pattern on an upper face side of a substrate; applying a first composition to a sidewall of the pattern; forming a resin layer by applying a second composition to an inner face side of the sidewall of the pattern coated with the first composition; allowing the resin layer to separate into a plurality of phases; and removing at least one of the plurality of phases. The first composition contains a first polymer. The second composition contains a second polymer. The second polymer includes a first block having a first structural unit and a second block having a second structural unit. The polarity of the second structural unit is higher than the polarity of the first structural unit. Immediately before forming of the resin layer, a static contact angle θ (°) of water on the sidewall of the pattern satisfies inequality (1). α ≥ θ ≥ α + β 2 ( 1 )

What is claimed is: 
     
         1 . A pattern-forming method comprising:
 forming a pattern on an upper face side of a substrate;   applying a first composition to a sidewall of the pattern;   forming a resin layer by applying a second composition to an inner face side of the sidewall of the pattern coated with the first composition;   allowing the resin layer to separate into a plurality of phases; and   removing at least one of the plurality of phases,   wherein   the first composition comprises a first polymer and a solvent,   the second composition comprises a second polymer and a solvent, the second polymer comprising a first block comprising a first structural unit and a second block comprising a second structural unit, a polarity of the second structural unit being higher than a polarity of the first structural unit, and   immediately before forming of the resin layer, a static contact angle θ (°) of water on the sidewall of the pattern satisfies an inequality (1):   
       
         
           
             
               
                 
                   
                     α 
                     ≥ 
                     θ 
                     ≥ 
                     
                       
                         α 
                         + 
                         β 
                       
                       2 
                     
                   
                 
                 
                   
                     ( 
                     1 
                     ) 
                   
                 
               
             
           
         
         wherein in the inequality (1), 
         α represents a static contact angle (°) of water on a film formed from a homopolymer comprising the first structural unit alone, and 
         β represents a static contact angle (°) of water on a film formed from a homopolymer comprising the second structural unit alone. 
       
     
     
         2 . The pattern-forming method according to  claim 1 , wherein the first polymer comprises the first structural unit. 
     
     
         3 . The pattern-forming method according to  claim 1 , wherein the first structural unit is derived from substituted or unsubstituted styrene. 
     
     
         4 . The pattern-forming method according to  claim 2 , wherein the second structural unit is derived from (meth)acrylic acid ester. 
     
     
         5 . The pattern-forming method according to  claim 2 , wherein the first polymer further comprises the second structural unit, a third structural or a combination thereof, the second structural unit and the third structural unit differing from each other in their structures except for a part derived from a polymerizable group. 
     
     
         6 . The pattern-forming method according to  claim 5 , wherein the first polymer comprises the first structural unit and the third structural unit. 
     
     
         7 . The pattern-forming method according to  claim 5 , wherein the third structural unit is derived from (meth)acrylic acid hydroxy hydrocarbon ester or (meth)acrylic acid sulfanyl hydrocarbon ester. 
     
     
         8 . The pattern-forming method according to  claim 5 , wherein the first polymer comprises the first structural unit and the second structural unit. 
     
     
         9 . The pattern-forming method according to  claim 5 , wherein the first polymer is a random copolymer. 
     
     
         10 . The pattern-forming method according to  claim 1 , wherein the first polymer is a homopolymer. 
     
     
         11 . The pattern-forming method according to  claim 1 , wherein the first polymer comprises a first group comprising a hydroxy group, a sulfanyl group or a combination thereof. 
     
     
         12 . The pattern-forming method according to  claim 11 , wherein the first group is bonded to at least one end of a main chain of the first polymer. 
     
     
         13 . The pattern-forming method according to  claim 6 , wherein the first polymer comprises a gradient polymer structure of the first structural unit and the third structural unit, and the third structural unit comprises a first group comprising a hydroxy group, a sulfanyl group or a combination thereof. 
     
     
         14 . The pattern-forming method according to  claim 1 , further comprising removing at least a part of a coating film formed on the sidewall from the first composition after applying the first composition. 
     
     
         15 . A pattern-forming method comprising:
 forming a hole pattern on an upper face side of a substrate;   applying a first composition to a sidewall of a hole of the hole pattern;   forming a resin layer by applying a second composition to the upper face side of the substrate and an inner face side of the sidewall of the hole coated with the first composition;   allowing the resin layer to separate into a plurality of phases; and   removing at least one of the plurality of phases,   wherein   the first composition comprises a first polymer and a solvent,   the second composition comprises a second polymer and a solvent, the second polymer comprising a first block comprising a first structural unit and a second block comprising a second structural unit, a polarity of the second structural unit being higher than a polarity of the first structural unit, and   immediately before forming of the resin layer, a static contact angle θ (°) of water on the sidewall of the hole satisfies an inequality (1):   
       
         
           
             
               
                 
                   
                     α 
                     ≥ 
                     θ 
                     ≥ 
                     
                       
                         α 
                         + 
                         β 
                       
                       2 
                     
                   
                 
                 
                   
                     ( 
                     1 
                     ) 
                   
                 
               
             
           
         
         wherein in the inequality (1), 
         α represents a static contact angle (°) of water on a film formed from a homopolymer comprising the first structural unit alone, and 
         β represents a static contact angle (°) of water on a film formed from a homopolymer comprising the second structural unit alone. 
       
     
     
         16 . The pattern-forming method according to  claim 15 , wherein the first polymer comprises the first structural unit. 
     
     
         17 . The pattern-forming method according to  claim 15 , wherein the first structural unit is derived from substituted or unsubstituted styrene. 
     
     
         18 . The pattern-forming method according to  claim 15 , wherein the second structural unit is derived from (meth)acrylic acid ester. 
     
     
         19 . The pattern-forming method according to  claim 16 , wherein the first polymer further comprises the second structural unit, a third structural or a combination thereof, the second structural unit and the third structural unit differing from each other in their structures except for a part derived from a polymerizable group. 
     
     
         20 . The pattern-forming method according to  claim 19 , wherein the first polymer comprises the first structural unit and the third structural unit. 
     
     
         21 . The pattern-forming method according to  claim 19 , wherein the third structural unit is derived from (meth)acrylic acid hydroxy hydrocarbon ester or (meth)acrylic acid sulfanyl hydrocarbon ester. 
     
     
         22 . The pattern-forming method according to  claim 19 , wherein the first polymer comprises the first structural unit and the second structural unit. 
     
     
         23 . The pattern-forming method according to  claim 19 , wherein the first polymer is a random copolymer. 
     
     
         24 . The pattern-forming method according to  claim 15 , wherein the first polymer is a homopolymer. 
     
     
         25 . The pattern-forming method according to  claim 15 , wherein the first polymer comprises a first group comprising a hydroxy group, a sulfanyl group or a combination thereof. 
     
     
         26 . The pattern-forming method according to  claim 25 , wherein the first group is bonded to at least one end of a main chain of the first polymer. 
     
     
         27 . The pattern-forming method according to  claim 20 , wherein the first polymer comprises a gradient polymer structure of the first structural unit and the third structural unit, and the third structural unit comprises a first group comprising a hydroxy group, a sulfanyl group or a combination thereof. 
     
     
         28 . The pattern-forming method according to  claim 15 , further comprising removing at least a part of a coating film formed on the sidewall from the first composition after applying the first composition. 
     
     
         29 . A structure comprising:
 a first layer comprising a first composition; and   a second layer comprising a second composition, the second layer being provided on the first layer,   wherein   the first composition comprises a first polymer and a solvent, and   the second composition comprises a second polymer and a solvent, the second polymer comprising a first block comprising a first structural unit and a second block comprising a second structural unit, a polarity of the second structural unit being higher than a polarity of the first structural unit,   the second layer is capable of separating into a plurality of phases, and   a static contact angle θ (°) of water on a surface of the first layer satisfies an inequality (1):   
       
         
           
             
               
                 
                   
                     α 
                     ≥ 
                     θ 
                     ≥ 
                     
                       
                         α 
                         + 
                         β 
                       
                       2 
                     
                   
                 
                 
                   
                     ( 
                     1 
                     ) 
                   
                 
               
             
           
         
         wherein in the inequality (1), 
         α represents a static contact angle (°) of water on a film formed from a homopolymer comprising the first structural unit alone, and 
         β represents a static contact angle (°) of water on a film formed from a homopolymer comprising the second structural unit alone. 
       
     
     
         30 . A structure comprising:
 a first layer having an annular shape and comprising a first composition; and   a second layer comprising a second composition, the second layer being provided on the first layer,   wherein   the first composition comprises a first polymer and a solvent, and   the second composition comprises a second polymer and a solvent, the second polymer comprising a first block comprising a first structural unit and a second block comprising a second structural unit, a polarity of the second structural unit being higher than a polarity of the first structural unit,   the second layer is capable of separating into a plurality of phases, and   a static contact angle θ (°) of water on a surface of the first layer satisfies an inequality (1):   
       
         
           
             
               
                 
                   
                     α 
                     ≥ 
                     θ 
                     ≥ 
                     
                       
                         α 
                         + 
                         β 
                       
                       2 
                     
                   
                 
                 
                   
                     ( 
                     1 
                     ) 
                   
                 
               
             
           
         
         wherein in the inequality (1), 
         α represents a static contact angle (°) of water on a film formed from a homopolymer comprising the first structural unit alone, and 
         β represents a static contact angle (°) of water on a film formed from a homopolymer comprising the second structural unit alone.