Organic anti-reflective coating material and its preparation

Abstract

Polymers are provided having the following formula I, II or III: Polymers of the present invention can be used to provide an anti-reflective coating (ARC) material useful for submicrolithography processes using 248 nm KrF, 193 nm ArF and 157 nm F 2 lasers. The polymers contain chromophore sub substituents which exhibit sufficient absorbance at wavelengths useful for such submicrolithography process. The ARC prevents back reflection from the surface of or lower layers in the semiconductor devices and solves the problem of the CD being altered by the diffracted and reflected light from such lower layers. The ARC also eliminates the standing waves and reflective notching due to the optical properties of lower layers on the wafer, and due to the changes in the thickness of the photosensitive film applied thereon. This results in the formation of stable ultrafine patterns suitable for 64M, 256M, 1G, 4G and 16G DRAM semiconductor devices and a great improvement in the production yield.

What is claimed is:  
     
         1 . 1. A 9-anthracene alkylacrylate compound, represented by the following chemical formula 39:  
       
         
           
           
               
               
           
         
       
       (chemical formula 39)  
       wherein, 
 R 1  is hydrogen or —CH 3 ;  
 R 1  to R 9 , which are the same or different, each represents hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, or a substituted or unsubstituted, linear or branched C 1 -C 6 alkyl, alkane, alkoxyalkyl or alkoxyalkane; and  
 m is an integer of 1 to 4.  
 
     
     
         2 . A method for preparing a 9-anthracene alkylacrylate compound which comprises reacting a 9-anthracene alkylalcohol with an acryloyl chloride compound in tetrahydrofuran, as shown in the following reaction formula 4:  
       
         
           
           
               
               
           
         
       
       (reaction formula 4)  
       wherein, R is hydrogen or —CH 3 ; R 1  to R 9 , which are the same or different, each represents hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, or a substituted or unsubstituted, linear or branched C 1 -C 6  alkyl, alkane, alkoxyalkyl or alkoxyalkane; and n is an integer of 1 to 4.  
     
     
         3 . 4-formylphenylmethacrylate, having the structure of the following chemical formula 40:  
       
         
           
           
               
               
           
         
       
       (chemical formula 40)  
     
     
         4 . A method for preparing 4-formylphenylmethacrylate which comprises reacting methacryloyl chloride with 4-hydroxybenzaldehyde.  
     
     
         5 . A polymer represented by the following general formula I:  
       
         
           
           
               
               
           
         
       
       (general formula I)  
       wherein, 
 R and R 1 , which are the same or different, each represents hydrogen or —CH 3 ;  
 R 1  to R 9 , which are the same or different, each represents hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, or a substituted or unsubstituted, linear or branched C 1 -C 6  alkyl, alkane, alkoxyalkyl or alkoxyalkane;  
 x and y each is a mole fraction in the range from 0.01 to 0.99; and  
 m is 1 or 2 and n is an integer of 2 to 4.  
 
     
     
         6 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x and y each is 0.5; and m is 1 and n is 2.  
     
     
         7 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x and y each is 0.5; and m is 1 and n is 3.  
     
     
         8 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x and y each is 0.5; and m is 1 and n is 4.  
     
     
         9 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is —CH 3 ; x and y each is 0.5; and m is 1 and n is 2.  
     
     
         10 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is —CH 3 ; x and y each is 0.5; and m is 1 and n is 3.  
     
     
         11 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is —CH 3 ; x and y each is 0.5; and m is 1 and n is 4.  
     
     
         12 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x and y each is 0.5; and m is 1 and n is 2.  
     
     
         13 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x and y each is 0.5; and m is 2 and n is 3.  
     
     
         14 . A polymer as set forth in  claim 5 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x and y each is 0.5; and m is 2 and n is 4.  
     
     
         15 . A method for preparing a copolymer (III) which comprises reacting a 9-anthracene alkylacrylate type monomer (I) with a hydroxyalkylacrylate type monomer (II) in the presence of an initiator in a solvent, as shown in the following reaction formula 5:  
       
         
           
           
               
               
           
         
       
       (reaction formula 5)  
       wherein, R; R 1  to R 9 ; and m and n have the meanings set forth in  claim 5 .  
     
     
         16 . A polymer represented by the following general formula II:  
       
         
           
           
               
               
           
         
       
       (general formula II)  
       wherein, 
 R, R I  and R II , which are the same or different, each is hydrogen or —CH 3 ;  
 R 1  to R 9 , which are the same or different, each represents hydrogen, hydroxy, methoxycarbonyl, carboxyl, hydroxymethyl, or a substituted or unsubstituted, linear or branched C 1 -C 6  alkyl, alkane, alkoxyalkyl or alkoxyalkane;  
 x, y and z each is an mole fraction in the range from 0.01 to 0.99; and  
 m is 1 or 2 and n is an integer of 2 to 4.  
 
     
     
         17 . A polymer as set forth in  claim 16 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x, y and z are 0.3, 0.5 and 0.2, respectively; and m is 1 and n is 2.  
     
     
         18 . A polymer as set forth in  claim 16 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x, y and z are 0.3, 0.5 and 0.2, respectively; and m is 1 and n is 3.  
     
     
         19 . A polymer as set forth in  claim 16 , wherein R 1 -R 9  each is hydrogen; R 1  is hydrogen; x, y and z are 0.3, 0.5 and 0.2, respectively; and m is 1 and n is 4.  
     
     
         20 . A polymer as set forth in  claim 16 , wherein R 1 -R 9  each is hydrogen; R 1  is —CH 3 ; x, y and z are 0.3, 0.5 and 0.2, respectively; and m is 1 and n is 2.  
     
     
         21 . A polymer as set forth in  claim 16 , wherein R 1 -R 9  each is hydrogen; R 1  is —CH 3 ; x, y and z are 0.3, 0.5 and 0.2; and m is 1 and n is 3.  
     
     
         22 . A polymer as set forth in  claim 16 , wherein R 1 -R 9  each is hydrogen; R 1  is —CH3; x, y and z are 0.3, 0.5 and 0.2, respectively; and m is 1 and n is 4.  
     
     
         23 . A method for preparing a copolymer (IV) which comprises reacting a 9-anthracene alkylacrylate type monomer (I), a hydroxyalkylacrylate type monomer (II) and methylmethacrylate (III) with each other in the presence of an initiator in a solvent, as shown in the following reaction formula 6:  
       
         
           
           
               
               
           
         
       
       (reaction formula 6)  
       wherein, 
 R, R I , and R III ; R1 to R9; and m and n have the meanings set forth in  claim 16 .  
 
     
     
         24 . A polymer having repeating units of the following general formula III:  
       
         
           
           
               
               
           
         
       
       (general formula III)  
       wherein, R III  is hydrogen or —CH 3  and R 0  is —CH 3  or —CH 2 CH 3 .  
     
     
         25 . A method for preparing a copolymer which comprises polymerizing formylphenylmethacrylate to form a polymer and then reacting said polymer with methanol or ethanol.  
     
     
         26 . A method as set forth in  claim 15  or  23 , wherein each of the monomers range, in mole fraction, from 0.01 to 0.99.  
     
     
         27 . A method as set forth in  claim 15  or  23 , wherein the initiator is selected from the group consisting of 2,2-azobisisobutyronitrile, acetylperoxide, laurylperoxide, and t-butylperoxide.  
     
     
         28 . A method as set forth in  claim 15  or  23 , wherein the solvent is selected from the group consisting of tetrahydrofuran, toluene, benzene, methylethyl ketone and dioxane.  
     
     
         29 . A method as set forth in  claim 15  or  23 , wherein the polymerization is carried out at a temperature of 50-90° C.  
     
     
         30 . An anti-reflective coating composition comprising a polymer of  claim 5 ,  16  or  24 .  
     
     
         31 . An anti-reflective coating composition as set forth in  claim 30 , further comprising an anthracene derivative.  
     
     
         32 . An anti-reflective coating composition as set forth in  claim 31 , wherein the anthracene derivative is selected from the group consisting of anthracene, 9-anthracene methanol, 9-anthracene carbonitrile, 9-anthracene carboxylic acid, dithranol, 1,2,10-anthracenetriol, anthraflavic acid, 9-anthraldehyde oxime, 9-anthraldehyde, 2-amino-7-methyl-5-oxo-5H-[1]-benzopyrano[2,3-b]pyridine-3-carbonitrile, 1-aminoanthraquinone, anthraquinone-2-carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9-anthryl trifluoromethyl ketone, 9-alkylanthracene derivatives represented by the following chemical formula 16, 9-carboxyl anthracene derivatives represented by the following chemical formula 17, 1-carboxyl anthracene derivatives represented by the following chemical formula 18, and the combination thereof:  
       
         
           
           
               
               
           
         
       
       (chemical formula 16) (chemical formula 17) (chemical formula 18)  
       wherein, R 11 , R 12 , R 13 , R 14 , and R 15 , which are the same or different, each represents —H, —OH, —CH 3 , —CH 2 OH, —(CH 2 )pCH 3  wherein p is an integer of 1 to 3, or a substituted or unsubstituted, linear or branched alkyl, alkane, alkoxyalkyl or alkoxyalkane containing 1-5 carbon atoms.  
     
     
         33 . A method for preparing an anti-reflective coating composition, which comprises dissolving a polymer of  claim 5 ,  16  or  24  in an organic solvent and then adding thereto, an anthracene derivative additive selected from the group consisting of anthracene, 9-anthracene methanol, 9-anthracene carbonitrile, 9-anthracene carboxylic acid, dithranol, 1,2,10-anthracenetriol, anthraflavic acid, 9-anthraldehyde oxime, 9-anthraldehyde, 2-amino-7-methyl-5-oxo-5H-[1]-benzopyrano[2,3-b )]pyridine-3-carbonitrile, 1-aminoanthraquinone, anthraquinone-2-carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9-anthryl trifluoromethyl ketone, 9-alkylanthracene derivatives of the following chemical formula 16, 9-carboxyl anthracene derivatives of the following chemical formula 17, 1-carboxyl anthracene derivatives of the following chemical formula 18, and combinations thereof.  
       
         
           
           
               
               
           
         
       
       (chemical formula 16) (chemical formula 17) (chemical formula 18)  
       wherein, R 11 , R 12 , R 13 , R 14  and R 15 , which are the same or different, each represents —H, —OH, —CH 3 , —CH 2 OH, —(CH 2 )pCH 3  wherein p is an integer of 1 to 3, or a substituted or unsubstituted, linear or branched alkyl, alkane, alkoxyalkyl or alkoxyalkane containing 1-5 carbon atoms.  
     
     
         34 . A method as set forth in  claim 33 , wherein the anthracene derivative additive is used at an amount of 0.1 to 30% by weight.  
     
     
         35 . A method as set forth in  claim 33 , wherein the organic solvent is selected from the group consisting of ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, cyclohexanone, and propyleneglycolmethyl ether acetate.  
     
     
         36 . An anti-reflective coating composition, comprising a polymer of either  claim 5  or  16 , and a polymer of  claim 24 .  
     
     
         37 . An anti-reflective coating composition as set forth in  claim 36 , further comprising an anthracene derivative.  
     
     
         38 . An anti-reflective coating composition as set forth in  claim 37 , wherein the anthracene derivative is selected from the group consisting of anthracene, 9-anthracene methanol, 9-anthracene carbonitrile, 9-anthracene carboxylic acid, dithranol, 1,2,10-anthracenetriol, anthraflavic acid, 9-anthraldehyde oxime, 9-anthraldehyde, 2-amino-7-methyl-5-oxo-5H-[1]-benzopyrano[2,3-b]pyridine-3-carbonitrile, 1-aminoanthraquinone, anthraquinone-2-carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9-anthryl trifluoromethyl ketone, 9-alkylanthracene derivatives of the following chemical formula 16, 9-carboxyl anthracene derivatives of the following chemical formula 17, 1-carboxyl anthracene derivatives of the following chemical formula 18, and combinations thereof:  
       
         
           
           
               
               
           
         
       
       (chemical formula 16) (chemical formula 17) (chemical formula 18)  
       wherein, R 11 , R 12 , R 13 , R 14  and R 15 , which are the same or different, each represents —H, —OH, —CH 3 , —CH 2 OH, —(CH 2 )pCH 3  wherein p is an integer of 1 to 3, or a substituted or unsubstituted, linear or branched alkyl, alkane, alkoxyalkyl or alkoxyalkane containing 1-5 carbon atoms.  
     
     
         39 . A method for preparing an anti-reflective coating composition, which comprises dissolving a mixture of a polymer of either  claim 5  or  16  and a polymer of  claim 24  in an organic solvent and then, adding thereto an anthracene derivative additive selected from the group consisting of anthracene, 9-anthracene methanol, 9-anthracene carbonitrile, 9-anthracene carboxylic acid, dithranol, 1,2,10-anthracenetriol, anthraflavic acid, 9-anthraldehyde oxime, 9-anthraldehyde, 2-amino-7-methyl-5-oxo-5H-[1]-benzopyrano [2,3-b]pyridine-3-carbonitrile, 1 -aminoanthraquinone, anthraquinone-2-carboxylic acid, 1,5-dihydroxyanthraquinone, anthrone, 9-anthryl trifluoromethyl ketone, 9-alkylanthracene derivatives of the following chemical formula 16, 9-carboxyl anthracene derivatives of the following chemical formula 17, 1-carboxyl anthracene derivatives of the following chemical formula 18, and combinations thereof.  
       
         
           
           
               
               
           
         
       
       (chemical formula 16) (chemical formula 17) (chemical formula 18) 
 wherein, R 11 ,R 12 , R 13 , R 14  and R 15 , which are the same or different, each represents —H, —OH, —CH 3 , —CH 2 OH, —(CH 2 )pCH 3  wherein p is an integer of 1 to 3, or a substituted or unsubstituted, linear or branched alkyl, alkane, alkoxyalkyl or alkoxyalkane containing 1-5 carbon atoms.  
 
     
     
         40 . A method as set forth in  claim 39 , wherein the anthracene derivative additive is used at an amount of 0.1 to 30% by weight.  
     
     
         41 . A method as set forth in  claim 39 , wherein the organic solvent is selected from the group consisting of ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, cyclohexanone, and propyleneglycolmethyl ether acetate.  
     
     
         42 . A method for forming an anti-reflective coating, in which an anti-reflective coating composition of  claim 30 ,  31 ,  36  or  37  is coated on a wafer and the wafer is subjected to hard baking at 80-300° C.  
     
     
         43 . A semiconductor device, fabricated by using an anti-reflective coating of  claim 30 ,  31 ,  36  or  37 .