Method for synthesizing polymeric azo dyes

Abstract

A method of coupling a diazonium salt with an organic polymer comprising, on order, the steps of: providing a polymer in one liquid phase; providing a diazonium salt in a separate liquid phase; contacting the separate phases, and thereby reacting the polymer and the diazonium salt.

What is claimed is:  
     
         1 . A process for producing an antireflective coating composition suitable for use in photolithography, comprising, in the following order: 
 a) providing an azo coupled polymer produced by a method comprising: 
 i) dissolving an organic polymer having a weight average molecular weight ranging from about 500 to 2,000,000 in a solvent, thereby providing one liquid phase;  
 ii) providing a diazonium salt in another solvent, thereby providing a separate liquid phase; and  
 iii) contacting the diazonium salt liquid phase and the organic polymer liquid phase, for a period of time that is greater than or equal to the minimum reaction time required to react said diazonium salt with said organic polymer; wherein said method further comprises intimately mixing the separate phases using an in-line mixing unit selected from: a static tubular reactor and a dynamic mixer; and  
   b) dissolving the azo coupled polymer from step a) in a solvent, and thereby producing an antireflective coating composition.    
     
     
         2 . The process of  claim 1 , wherein said polymer has a weight average molecular weight ranging from about 3000 to 1,000,000.  
     
     
         3 . The process of  claim 1 , wherein said polymer has a weight average molecular weight from about 5000 to 80,000.  
     
     
         4 . The process of  claim 1 , wherein said synthetic organic polymer contains at least one of the following moieties:  
       
         
           
           
               
               
           
         
       
       where, 
 R 1  is selected from a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, or a group having the structure:  
                     
 where,  
 A 1  and A 2  are independently selected from the group: halo, —CN, —COZ, —COOZ, —CONHZ, —CONZ 2 , —SO 2 NHZ, —SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1 -C 10 ) alkyl, (C 1 C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, substituted or unsubstituted carbocyclic, aromatic or heterocyclic group, or may be —COOM, —SO 3 M, where M is alkali metal, ammonium, alkyl ammonium;  
 or A 1  and A 2  are combined to form a 3-10 membered substituted or unsubstituted carbocyclic or heterocyclic ring containing an α-carbonyl group said polymer optionally further comprising one or more co-monomer moieties having a structure:  
                     
 where,  
 R 6 -R 9  are independently either halo, —O(CH 2 ) x —OH (where x=1-10), O(CH 2 CH 2 ) y —OH, —(OCH 2 CH 2 ) Y —OH (where y=0-10), —CN, Z, —OZ, —OCOZ, —COZ, —COOZ, —NHZ, —NZ 2 —NHCOZ, —CONHZ, —CONZ 2 , SZ, —SO 3 Z, —SO 2 NHZ, —SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1 -C 10 ) alkyl, (C 1 -C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, 3-10 membered substituted or unsubstituted carbocyclic or heterocyclic group. , or R 8  and R 9  are combined to form a 3-10 membered carbocyclic or heterocyclic ring.  
 
     
     
         5 . The process of  claim 4 , wherein said organic polymer additionally comprises one or more moieties selected from (1):  
       
         
           
           
               
               
           
         
       
       where, 
 R 1′ -R 3′ and R 4  are independently either halo, nitro, —O(CH 2 ) x —OH, —O(CH 2 CH 2 ) x OH (where x=1-10), —(OCH 2 CH 2 ) y —OH (where y=0-10),—CN, Z, —OZ, —OCOZ, —COZ, —COOZ, —NHZ, —NZ 2 , —NHCOZ, —CONHZ, —NZCOZ, —CONZ 2 , SZ, —SO 3 Z, —SO 2 NHZ, —SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1 -C 10 ) alkyl, (C 1 -C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, 3-10 membered substituted or unsubstituted carbocyclic or heterocyclic group; or —COOM, —SO 3 M, where M is alkali metal, ammonium, alkyl ammonium, or R 1′  and R 2′  are combined to form a 3-10 membered carbocyclic or heterocyclic ring;  
 m=0-4;  
 or (2):  
                     
 where,  
 R 1″ -R 3″  are independently either —Z, —OZ, —OCOZ, —COZ, —COOZ, —NHZ, —NZ 2 , —NHCOZ, —CONHZ, —NZCOZ, —CONZ 2 , —SZ, —SO 3 Z, —SO 2 NHZ, —SO 2 NZ 2 , SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1 -C 10 ) alkyl, (C 1 -C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, a substituted or unsubstituted carbocyclic or heterocyclic ring, or R 1 ″ and R 2 ″ are combined to form a 3-10 membered carbocyclic or heterocyclic ring,  
 A 1  and A 2  are independently selected from the group: halo, —CN, —Z, —OCOZ, —COZ, —COOZ, NHZ, —NZ 2 , —NHCOZ, —CONHZ, —NZCOZ, —CONZ 2 , —SZ, SO 3 Z, —SO 2 NHZ, —SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1-C   10 ) alkyl, (C 1 -C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, 3-10 membered substituted or unsubstituted carbocyclic or heterocyclic ring; or —COOM, —SO 3 M, where M is alkali metal, ammonium, alkyl ammonium; or  
 A 1  and A 2  are combined to form a 3-10 membered substituted or unsubstituted carbocyclic or heterocyclic ring containing an α-carbonyl group.  
 
     
     
         6 . The process of  claim 1 , wherein said diazonium salt has the general structure:  
       ArN 2   + X −   
       where, 
 Ar is an aryl group X is selected from the group consisting of Cl, Br, —NO 3 , —HSO 4 , —OCOCH 3 , and  
 —OH.  
 
     
     
         7 . The process of  claim 1 , wherein said diazonium salt is derived from an aryl amino acid or an amino substituted aromatic compound.  
     
     
         8 . The process of  claim 1 , wherein said organic polymer is a vinyl polymer.  
     
     
         9 . A process of forming an image on a substrate comprising, in the following order, the steps of: 
 a) providing an antireflective coating composition prepared by the method of  claim 1;     b) either before or after coating a photoresist composition onto a suitable substrate, coating the antireflective coating composition from step a) onto said suitable substrate;    c) heating the coated substrate from step b), and thereby substantially removing the photoresist solvent;    d) imagewise exposing the photoresist composition;    e) developing the imagewise exposed photoresist composition.    
     
     
         10 . The process of  claim 9 , wherein the photoresist composition comprises a novolak resin, a photosensitive compound and a solvent.  
     
     
         11 . The process of  claim 9 , wherein the photoresist composition comprises a substituted polyhydroxystyrene, a photoactive component and a solvent.  
     
     
         12 . The process of  claim 9 , wherein said synthetic organic polymer contains one or more moieties selected from ( 1   a ):  
       
         
           
           
               
               
           
         
       
       where, 
 R 1′ -R 3′  and R 4  are independently either halo, nitro, —O(CH 2 ) x —OH, —O(CH 2 CH 2 ) x —OH (where x=1-10),, —(OCH 2 CH 2 ) y —OH (where y=0−10), —CN, Z, —OZ, —OCOZ, —COZ, —COOZ, —NHZ, —NZ 2 , —NHCOZ, —CONHZ, —NZCOZ, —CONZ 2 , SZ, —SO 3 Z, —SO 2 NHZ, —SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1 -C 10 ) alkyl, (C 1 -C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, 3-10 membered substituted or unsubstituted carbocyclic or heterocyclic group, or  
 —COOM, —SO 3 M, where M is alkali metal, ammonium, alkyl ammonium, or R 1′  and R 2′  are combined to form a 3-10 membered carbocyclic or heterocyclic ring;  
 m=0-4;  
 or ( 2   a ):  
                     
 where,  
 R 1″ -R 3″  are independently either Z, —OZ, —OCOZ, —COZ, —COOZ, —NHZ, —NZ 2 ,—NHCOZ, —CONHZ, —NZCOZ, —CONZ 2 , SZ, —SO 3 Z, —SO 2 NHZ, —SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1 -C 10 ) alkyl, (C 1 -C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, 3-10 membered substituted or unsubstituted heterocyclic group, or R 1 ″ and R 2 ″ combined to form a 3-10 membered carbocyclic or heterocyclic group;  
 X 1  and X 2  are independently —CO—, —OC(O)—, —CONH—O—, aryl, —(CH 2 CH 2 O) y — (where y=0-10), (C 1 -C 10 ) alkyl, cyclohexyl, —S—, —S (C 1 -C 10 ) alkyl , —O (C 1 -C 10 ) alkyl, —NH—, —N (C 1 -C 10 ) alkyl, or (C 1 -C 10 ) hydroxyalkyl,  
 n is independently 0-2,  
 A 1′  and A 2′  are independently selected from the group: halo, —CN, —COZ, —COOZ, —CONHZ, —CONZ 2 , —SO 2 NHZ, —SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1 -C 10 ) alkyl, (C 1 -C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, a substituted or unsubstituted carbocyclic, aromatic or heterocyclic group, or may be —COOM, —SO 3 M, where M is alkali metal, ammonium, alkyl ammonium; or  
 A 1  and A 2  are combined to form a 3-10 membered substituted or unsubstituted carbocyclic or heterocyclic ring containing an α-carbonyl group; said polymer optionally having one or more co-monomer moieties of the formula:  
                     
 where,  
 R 6 -R 9  are independently either halo, —O(CH 2 ) x —OH, —O(CH 2 CH 2 ) x —OH (where x=1-10), —(OCH 2 CH 2 ) y —OH (where y=0-10), —CN, Z, —OZ, —OCOZ, —COZ, —COOZ, —NHZ, —NZ 2 , —NHCOZ, —NZCOZ, —CONHZ,—CONZ 2 , —SZ, —SO 3 Z, —SO 2 NHZ, —SO 2 NZ 2 , —SO 2 Z, —SO 2 CF 3 , where Z is H, (C 1 -C 10 ) alkyl, (C 1 -C 10 ) hydroxyalkyl, (C 1 -C 10 ) alkoxyl, (C 1 -C 10 ) fluoroalkyl, (C 1 -C 10 ) epoxyalkyl, (C 1 -C 10 ) alkenyl, 3-10 membered substituted or unsubstituted carbocyclic or heterocyclic group, or  
 —COOM,—SO 3 M, where M is alkali metal, ammonium, alkyl ammonium, or R 8  and R 9  are combined to form a 3-10 membered carbocyclic or heterocyclic ring.