Mask patterns including gel layers for semiconductor device fabrication and methods of forming the same

Abstract

Mask patterns include a resist pattern and a gel layer on a surface of the resist pattern having a junction including hydrogen bonds between a proton donor polymer and a proton acceptor polymer. Methods of forming the mask patterns and methods of fabricating a semiconductor device using the mask patterns as etching masks are also provided.

1 . A mask pattern comprising: 
 a resist pattern; and    a gel layer on a surface of the resist pattern having a junction comprising hydrogen bonds between a proton donor polymer and a proton acceptor polymer.    
   
   
       2 . The mask pattern of  claim 1 , wherein the gel layer is water insoluble.  
   
   
       3 . The mask pattern of  claim 1 , wherein the junction of the gel layer comprises: 
 a plurality of regions capable of undergoing hydrogen bonding and wherein the proton donor polymer and the proton acceptor polymer are hydrogen bonded therebetween; and    a defect region wherein the proton donor polymer and the proton acceptor polymer are not hydrogen-bonded therebetween so as to form a region lacking hydrogen bonding between the hydrogen-bonded regions.    
   
   
       4 . The mask pattern of  claim 3 , wherein the proton donor polymer of the defect region comprises a —COO −  group.  
   
   
       5 . The mask pattern of  claim 3 , wherein the proton donor polymer of the defect region comprises a —COOR group, wherein R is a substituted or unsubstituted C 1  to C 20  hydrocarbon group or a substituted or unsubstituted C 1  to C 20  acid-labile group.  
   
   
       6 . The mask pattern of  claim 5 , wherein R is an acid-labile group.  
   
   
       7 . The mask pattern of  claim 5 , wherein R is a group comprising silicon.  
   
   
       8 . The mask pattern of  claim 5 , wherein R is methyl, acetyl(isopropyl)(2-methyl-butan-3-on-2-yl), t-butyl, isonorbonyl, 2-metyl-2-adamantyl, 2-ethyl-2-adamantyl, 3-tetrahydrofuranyl, 3-oxocyclohexyl, γ-butyllactone-3-yl, mavaloniclactone, γ-butyrolactone-2-yl, 3-methyl-γ-butyrolactone-3-yl, 2-tetrahyd ropyranyl, 2-tetrahyd rofuranyl, 2,3-propylenecarbonate-1-yl, 1-methoxyethyl, 1-ethoxyethyl, 1-(2-methoxyethoxy)ethyl, 1-(2-acetoxyethoxy)ethyl, t-buthoxycarbonylmethyl, methoxymethyl, ethoxymethyl, trimethoxysilyl or triethoxysilyl.  
   
   
       9 . The mask pattern of  claim 1 , wherein the proton donor polymer comprises a monomer repeat unit comprising a —COOH or —COOR group wherein R is a substituted or unsubstituted C 1  to C 20  hydrocarbon group or a substituted or unsubstituted C 1  to C 20  acid-labile group.  
   
   
       10 . The mask pattern of  claim 9 , wherein the proton donor polymer comprises a first repeat unit comprising at least one of an acrylic acid monomer unit according to formula 1 and a maleic acid monomer unit according to formula 2:  
     
       
         
         
             
             
         
       
       wherein R 1  is hydrogen or a methyl group;  
       R 2 , R 3 , and R 4  are each independently hydrogen, a substituted or unsubstituted C 1  to C 20  hydrocarbon or a substituted or unsubstituted C 1  to C 20  acid-labile group.  
     
   
   
       11 . The mask pattern of  claim 10 , wherein the proton donor polymer further comprises a second repeat unit comprising at least one of an acrylamide monomer unit, a vinyl monomer unit, an alkyleneglycol monomer unit, an anhydrous maleic acid monomer unit, an ethyleneimine monomer unit, an oxazoline group-containing monomer unit, an acrylonitrile monomer unit, an allylamide monomer unit, a 3,4-dihydropyrane monomer unit or a 2,3-dihydrofuran monomer unit.  
   
   
       12 . The mask pattern of  claim 1 , wherein the proton donor polymer has a weight average molecular weight in a range of about 1,000 to about 100,000 daltons.  
   
   
       13 . The mask pattern of  claim 1 , wherein the proton acceptor polymer comprises a first repeat unit comprising a monomer unit having an amido group.  
   
   
       14 . The mask pattern of  claim 13 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl monomer unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein R 5  is hydrogen or a methyl group;  
       R 6  and R 7  are each independently hydrogen or C 1  to C 5  alkyl, and R 6  and R 7  can be connected in the form of —R 6 —R 7  to form a cyclic structure.  
     
   
   
       15 . The mask pattern of  claim 14 , wherein the proton acceptor polymer comprises a first repeat unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein n is an integer of 1 to 8.  
     
   
   
       16 . The mask pattern of  claim 15 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl pyrrolidone monomer unit.  
   
   
       17 . The mask pattern of  claim 15 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl caprolactam monomer unit.  
   
   
       18 . The mask pattern of  claim 1 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl monomer unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein R 8  is hydrogen or a methyl group; and  
       R 9  and R 10  are each independently hydrogen, methyl, an n-propyl group, or an i-propyl group.  
     
   
   
       19 . The mask pattern of  claim 13 , wherein the proton acceptor polymer further comprises a second repeat unit comprising at least one of an acrylic monomer unit, a vinyl monomer unit, an alkyleneglycol monomer unit, an ethyleneimine monomer unit, an oxazoline group-containing monomer unit, an acrylonitrile monomer unit, an allylamide monomer unit, a 3,4-dihydropyrane monomer unit or a 2,3-dihydrofuran monomer unit.  
   
   
       20 . The mask pattern of  claim 1 , wherein the proton acceptor polymer has a weight average molecular weight in a range of about 1,000 to about 100,000 daltons.  
   
   
       21 . The mask pattern of  claim 1 , wherein the gel layer further comprises a surfactant.  
   
   
       22 . The mask pattern of  claim 1 , wherein the resist pattern comprises a material comprising a phenol-formaldehyde (Novolac) resin and/or a diazonaphthoquinone (DNQ)-based compound.  
   
   
       23 . The mask pattern of  claim 1 , wherein the resist pattern is formed using a chemically amplified resist composition comprising a photo-acid generator (PAG).  
   
   
       24 . The mask pattern of  claim 1 , wherein the resist pattern is formed using a resist composition suitable for use with a g-line, an i-line, a KrF excimer laser (about 248 nm), an ArF excimer laser (about 193 nm), an F 2  excimer laser (about 157 nm) and/or e-beams.  
   
   
       25 . The mask pattern of  claim 1 , wherein the resist pattern is formed using a positive-type resist composition or a negative-type resist composition.  
   
   
       26 . The mask pattern of  claim 1 , wherein the resist pattern is formed with a plurality of openings defining a hole pattern.  
   
   
       27 . The mask pattern of  claim 1 , wherein the resist pattern is formed with a plurality of lines defining a line and space pattern.  
   
   
       28 . A method of forming a mask pattern comprising: 
 forming a resist pattern on a substrate; and    forming on a surface of the resist pattern, a gel layer having a junction formed by hydrogen bonding between a proton donor polymer and a proton acceptor polymer.    
   
   
       29 . The method of  claim 28 , wherein forming the gel layer comprises: 
 preparing a coating composition comprising the proton donor polymer, the proton acceptor polymer, and/or a base;    contacting the coating composition with the surface of the resist pattern; and    heating the resist pattern to an extent wherein the coating composition is contacted with the surface of the resist pattern to diffuse an acid of the resist pattern into the coating composition.    
   
   
       30 . The method of  claim 29 , wherein preparing the coating composition comprises: 
 preparing a first aqueous solution comprising the proton acceptor polymer and/or the base; and    adding a second aqueous solution comprising the proton donor polymer to the first aqueous solution to obtain a mixed solution.    
   
   
       31 . The method of  claim 30 , wherein preparing the coating composition further comprises ultrasonically treating the mixed solution comprising the first aqueous solution and the second aqueous solution to remove a precipitate or a hydrogel from the coating composition.  
   
   
       32 . The method of  claim 30 , wherein preparing the coating composition further comprises filtering the mixed solution comprising the first aqueous solution and the second aqueous solution.  
   
   
       33 . The method of  claim 30 , wherein the base comprises an amine, tetramethylammonium hydroxide or tetraethylammonium hydroxide.  
   
   
       34 . The method of  claim 30 , wherein the base is used in an amount in a range of about 0.1 to about 5.0 wt %, based on the total weight of the coating composition.  
   
   
       35 . The method of  claim 30 , wherein the first aqueous solution further comprises an additive comprising an alcohol, ether, primary amine, secondary amine, tertiary amine or an organic salt.  
   
   
       36 . The method of  claim 29 , wherein the coating composition comprises the proton donor polymer and the proton acceptor polymer mixed at a weight ratio of about 1:9 to about 9:1.  
   
   
       37 . The method of  claim 29 , wherein the coating composition further comprises a surfactant and/or an acid.  
   
   
       38 . The method of  claim 37 , wherein the surfactant and/or the acid are each used in an amount in a range of about 0.01 to about 0.5 wt %, based on the total weight of the coating composition.  
   
   
       39 . The method of  claim 29 , wherein the proton donor polymer and the proton acceptor polymer are each used in an amount in a range of about 0.1 to about 5.0 wt %, based on the total weight of the coating composition.  
   
   
       40 . The method of  claim 29 , wherein the proton donor polymer comprises a monomer repeat unit comprising a —COOH or —COOR group, wherein R is a substituted or unsubstituted C 1  to C 20  hydrocarbon.  
   
   
       41 . The method of  claim 40 , wherein the proton donor polymer comprises a first repeat unit comprising at least one of an acrylic acid monomer unit according to formula 1 and a maleic acid monomer unit according to formula 2:  
     
       
         
         
             
             
         
       
       wherein R 1  is hydrogen or a methyl group;  
       R 2 , R 3 , and R 4  are each independently hydrogen, a substituted or unsubstituted C 1  to C 20  hydrocarbon or a substituted or unsubstituted C 1  to C 20  acid-labile group.  
     
   
   
       42 . The method of  claim 41 , wherein the proton donor polymer further comprises a second repeat unit comprising at least one of an acrylamide monomer unit, a vinyl monomer unit, an alkyleneglycol monomer unit, an anhydrous maleic acid monomer unit, an ethyleneimine monomer unit, an oxazoline group-containing monomer unit, an acrylonitrile monomer unit, an allylamide monomer unit, a 3,4-dihydropyrane monomer unit or a 2,3-dihydrofuran monomer unit.  
   
   
       43 . The method of  claim 29 , wherein the proton donor polymer has a weight average molecular weight in a range of about 1,000 to about 100,000 daltons.  
   
   
       44 . The method of  claim 29 , wherein the proton acceptor polymer comprises a first repeat unit comprising a monomer unit having an amido group.  
   
   
       45 . The method of  claim 44 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl monomer unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein R 5  is hydrogen or a methyl group;  
       R 6  and R 7  are each independently hydrogen or C 1  to C 5  alkyl, and R 6  and R 7  can be connected in the form of —R 6 —R 7  to form a cyclic structure.  
     
   
   
       46 . The method of  claim 45 , wherein the proton acceptor polymer comprises a first repeat unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein n is an integer of 1 to 8.  
     
   
   
       47 . The method of  claim 46 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl pyrrolidone monomer unit.  
   
   
       48 . The method of  claim 46 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl caprolactam monomer unit.  
   
   
       49 . The method of  claim 29 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl monomer unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein R 8  is hydrogen or methyl; and  
       R 9  and R 10  are each independently hydrogen, methyl, an n-propyl group or an i-propyl group.  
     
   
   
       50 . The method of  claim 44 , wherein the proton acceptor polymer further comprises a second repeat unit comprising at least one of an acrylic monomer unit, a vinyl monomer unit, an alkyleneglycol monomer unit, an ethyleneimine monomer unit, an oxazoline group-containing monomer unit, an acrylonitrile monomer unit, an allylamide monomer unit, a 3,4-dihydropyrane monomer unit or a 2,3-dihydrofuran monomer unit.  
   
   
       51 . The method of  claim 29 , wherein the proton acceptor polymer has a weight average molecular weight in a range of about 1,000 to about 100,000 daltons.  
   
   
       52 . The method of  claim 29 , wherein heating the resist pattern is performed at a temperature in a range of about 120° C. to about 170° C.  
   
   
       53 . The method of  claim 29 , further comprising using deionized water to remove the coating composition remaining on the gel layer after formation of the gel layer.  
   
   
       54 . A method of fabricating a semiconductor device comprising: 
 forming an underlayer on a semiconductor substrate;    forming a resist pattern having defined regions through which the underlayer is exposed;    forming on a surface of the resist pattern a gel layer having a junction formed by hydrogen bonding between a proton donor polymer and a proton acceptor polymer; and    etching the underlayer using the resist pattern and the gel layer as an etching mask.    
   
   
       55 . The method of  claim 54 , wherein forming the gel layer comprises: 
 preparing a coating composition comprising the proton donor polymer, the proton acceptor polymer, and/or a base;    contacting the coating composition with a surface of the resist pattern; and    heating the resist pattern to an extent wherein the coating composition is contacted with the surface of the resist pattern to diffuse an acid of the resist pattern into the coating composition.    
   
   
       56 . The method of  claim 55 , wherein preparing the coating composition comprises: 
 preparing a first aqueous solution comprising the proton acceptor polymer and/or the base; and    adding a second aqueous solution comprising the proton donor polymer to the first aqueous solution to obtain a mixed solution.    
   
   
       57 . The method of  claim 56 , wherein preparing the coating composition further comprises ultrasonically treating the mixed solution comprising the first aqueous solution and the second aqueous solution to remove a precipitate or a hydrogel from the coating composition.  
   
   
       58 . The method of  claim 56 , wherein preparing the coating composition further comprises filtering the mixed solution comprising the first aqueous solution and the second aqueous solution.  
   
   
       59 . The method of  claim 56 , wherein the base comprises an amine, tetramethylammonium hydroxide or tetraethylammonium hydroxide.  
   
   
       60 . The method of  claim 56 , wherein the base is used in an amount in a range of about 0.1 to about 5.0 wt %, based on the total weight of the coating composition.  
   
   
       61 . The method of  claim 56 , wherein the first aqueous solution further comprises an additive comprising an alcohol, ether, primary amine, secondary amine, tertiary amine or an organic salt.  
   
   
       62 . The method of  claim 55 , wherein the coating composition comprises the proton donor polymer and the proton acceptor polymer mixed at a weight ratio of about 1:9 to about 9:1.  
   
   
       63 . The method of  claim 55 , wherein the coating composition further comprises a surfactant and/or an acid.  
   
   
       64 . The method of  claim 63 , wherein the surfactant and/or the acid are each used in an amount in a range of about 0.01 to about 0.5 wt %, based on the total weight of the coating composition.  
   
   
       65 . The method of  claim 55 , wherein the proton donor polymer and the proton acceptor polymer are each used in an amount in a range of about 0.1 to about 5.0 wt %, based on the total weight of the coating composition.  
   
   
       66 . The method of  claim 55 , wherein the proton donor polymer comprises a monomer repeat unit comprising a —COOH or —COOR group, wherein R is a substituted or unsubstituted C 1  to C 20  hydrocarbon group.  
   
   
       67 . The method of  claim 66 , wherein the proton donor polymer comprises a first repeat unit comprising at least one of an acrylic acid monomer unit according to formula 1 and a maleic acid monomer unit according to formula 2:  
     
       
         
         
             
             
         
       
       wherein R 1  is hydrogen or a methyl group;  
       R 2 , R 3 , and R 4  are each independently hydrogen, a substituted or unsubstituted C 1  to C 20  hydrocarbon or a substituted or unsubstituted C 1  to C 20  acid-labile group.  
     
   
   
       68 . The method of  claim 67 , wherein the proton donor polymer further comprises a second repeat unit comprising at least one of an acrylamide monomer unit, a vinyl monomer unit, an alkyleneglycol monomer unit, an anhydrous maleic acid monomer unit, an ethyleneimine monomer unit, an oxazoline group-containing monomer unit, an acrylonitrile monomer unit, an allylamide monomer unit, a 3,4-dihydropyrane monomer unit or a 2,3-dihydrofurane monomer unit.  
   
   
       69 . The method of  claim 55 , wherein the proton donor polymer has a weight average molecular weight in a range of about 1,000 to about 100,000 daltons.  
   
   
       70 . The method of  claim 55 , wherein the proton acceptor polymer comprises a first repeat unit comprising a monomer unit having an amido group.  
   
   
       71 . The method of  claim 70 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl monomer unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein R 5  is hydrogen or a methyl group;  
       R 6  and R 7  are each independently hydrogen or C 1  to C 5  alkyl, and R 6  and R 7  can be connected in the form of —R 6 —R 7  to form a cyclic structure.  
     
   
   
       72 . The method of  claim 71 , wherein the proton acceptor polymer comprises a first repeat unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein n is an integer of 1 to 8.  
     
   
   
       73 . The method of  claim 72 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl pyrrolidone monomer unit.  
   
   
       74 . The method of  claim 72 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl caprolactam monomer unit.  
   
   
       75 . The method of  claim 55 , wherein the proton acceptor polymer comprises a first repeat unit comprising a vinyl monomer unit according to the following formula:  
     
       
         
         
             
             
         
       
       wherein R 8  is hydrogen or methyl; and  
       R 9  and R 10  are each independently hydrogen, methyl, an n-propyl group or an i-propyl group.  
     
   
   
       76 . The method of  claim 70 , wherein the proton acceptor polymer further comprises a second repeat unit comprising at least one of an acrylic monomer unit, a vinyl monomer unit, an alkyleneglycol monomer unit, an ethyleneimine monomer unit, an oxazoline group-containing monomer unit, an acrylonitrile monomer unit, an allylamide monomer unit, a 3,4-dihydropyrane monomer unit or a 2,3-dihydrofuran monomer unit.  
   
   
       77 . The method of  claim 55 , wherein the proton acceptor polymer has a weight average molecular weight in a range of about 1,000 to about 100,000 daltons.  
   
   
       78 . The method of  claim 55 , wherein heating the resist pattern is performed at a temperature in a range of about 120° C. to about 170° C.  
   
   
       79 . The method of  claim 55 , further comprising using deionized water to remove a coating composition remaining on the gel layer after formation of the gel layer.  
   
   
       80 . The method of  claim 54 , wherein the resist pattern comprises a material comprising a phenol-formaldehyde (Novolac) resin and/or a DNQ-based compound.  
   
   
       81 . The method of  claim 54 , wherein the resist pattern is formed using a chemically amplified resist composition comprises a photo-acid generator (PAG).  
   
   
       82 . The method of  claim 54 , wherein the resist pattern is formed using a resist composition suitable for use with a g-line, an i-line, a KrF excimer laser (about 248 nm), an ArF excimer laser (about 193 nm), an F 2  excimer laser (about 157 nm), and/or e-beams.  
   
   
       83 . The method of  claim 54 , wherein the resist pattern is formed using a positive-type resist composition or a negative-type resist composition.  
   
   
       84 . The method of  claim 54 , wherein the resist pattern is formed with a plurality of openings defining a hole pattern.  
   
   
       85 . The method of  claim 54 , wherein the resist pattern is formed with a plurality of lines defining a line and space pattern.  
   
   
       86 . The method of  claim 54 , wherein the underlayer film comprises dielectric film, a conductive film, a semiconductive film and/or a resist film.