Organic anti-reflective coating compositions for advanced microlithography

Abstract

New polymers and new anti-reflective compositions containing such polymers are provided. The compositions comprise a polymer (e.g., epoxy cresol novolac resins) bonded with a chromophore (4-hydroxybenzoic acid, trimellitic anhydride). The inventive compositions can be applied to substrates (e.g., silicon wafers) to form anti-reflective coating layers having high etch rates which minimize or prevent reflection during subsequent photoresist exposure and developing.

1. In an anti-reflective composition comprising a polymer and a vinyl ether crosslinking agent dispersed in a solvent system, the improvement being that said polymer comprises recurring monomers according to the formula 
                 
 
       wherein:
 each R is individually selected from the group consisting of —OH, —H, and alkyl groups; and  
 X is an aromatic or heterocyclic light-absorbing moiety and if none of R is —OH, then X includes an —OH.  
 
     
     
       2. The composition of  claim 1 , wherein X includes an aromatic portion selected from the group consisting of thiophenes, napthoic acid, anthracene, naphthalene, benzene, chalcone, phthalimides, pamoic acid, acridine, azo compounds, dibenzofuran, and derivatives thereof. 
     
     
       3. The composition of claim  2    1 , wherein X has a formula selected from the group consisting of 
                 
 
       wherein R 1  is selected from the group consisting of —H and alkyl groups. 
     
     
       4. The composition of  claim 1 , wherein   is selected from the group consisting of acrylics, polyesters, epoxy novolacs, polysaccharides, polyethers, polyimides, and mixtures thereof. 
     
     
       5. The composition of  claim 1 , wherein said polymer has an average molecular weight of from about 3,000-60,000 Daltons. 
     
     
       6. The composition of  claim 1 , wherein X is present in said polymer at a level of from about 10-60% by weight, based upon the total weight of the polymer taken as 100% by weight. 
     
     
       7. The composition of  claim 1 , wherein said composition further comprises a compound selected from the group consisting of crosslinking agents,  catalysts, and mixtures thereof . 
     
     
       8. The composition of  claim 7 , wherein said compound is a crosslinking agent selected from the group consisting of aminoplasts, epoxies, polyols, anhydrides, glycidyl ethers, vinyl ethers, and mixtures thereof. 
     
     
       9. The composition of claim  8    1 , wherein said crosslinking agent is selected from the group consisting of glycourils, melamines,  trimethylolpropane trivinylether, and trimethylolpropane triglycidylether . 
     
     
       10. The composition of  claim 7 , wherein said compound is a  catalyst is selected from the group consisting of p-toluenesulfonic acid, Bisphenol S, and mixtures thereof. 
     
     
       11. The composition of  claim 1 , wherein said solvent system includes a solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and mixtures thereof. 
     
     
       12. A cured anti-reflective layer comprising a crosslinked polymer including recurring monomers having a formula 
                 
 
       wherein:
 each R is individually selected from the group consisting of —OH, —H, and alkyl groups;  
 X is an aromatic or heterocyclic light-absorbing moiety; and  
 at least one of X or R is, or comprises, an —OR 2  group, where R 2  is a vinyl ether crosslinking group.  
 
     
     
       13. The layer of  claim 12 , wherein X includes an aromatic portion selected from the group consisting of thiophenes, naphthoic acid, anthracene, naphthalene, benzene, chalcone, phthalimides, pamoic acid, acridine, azo compounds, dibenzofuran, and derivatives thereof. 
     
     
       14. The layer of claim  13    12 , wherein X has a formula selected from the group consisting of: 
                 
 
       wherein R 1  is selected from the group consisting of —H and alkyl groups. 
     
     
       15. The layer of  claim 12 , wherein   is selected from the group consisting of acrylics, polyesters, epoxy novolacs, polysaccharides, polyethers, polyimides, and mixtures thereof. 
     
     
       16. The layer of  claim 12 , wherein said polymer has an average molecular weight of from about 3,000-60,000 Daltons. 
     
     
       17. The layer of  claim 12 , wherein X is present in said polymer at a level of from about 10-60% by weight, based upon the total weight of the polymer taken as 100% by weight. 
     
     
       18. The layer of  claim 12 , wherein said layer is adjacent a substrate. 
     
     
       19. The layer of  claim 18 , wherein said substrate is selected from the group consisting of Si, Al, W, WSi, GaAs, SiGe, Ta, and TaN wafers. 
     
     
       20. The layer of  claim 18 , wherein R 2  is selected from the group consisting of moieties of glycourils, melamines,  trimethylolpropane trivinylether, and trimethylolpropane triglycidylether . 
     
     
       21. A method of using an anti-reflective composition, said method comprising the step of applying a quantity of the composition according to  claim 1  to a substrate to form a layer thereon. 
     
     
       22. The method of  claim 21 , wherein said applying step comprises spin-coating said composition onto said substrate surface. 
     
     
       23. The method of  claim 21 , wherein said substrate has a hole formed therein, said hole being defined by a bottom wall and sidewalls, and said applying step comprises applying said composition to at least a portion of said bottom wall and sidewalls. 
     
     
       24. The method of  claim 21 , further including the step of baking said layer, after said applying step, at a temperature of from about 115-205° C. to yield a cured layer. 
     
     
       25. The method of  claim 24 , further including the step of applying a photoresist to said baked layer. 
     
     
       26. The method of  claim 25 , further including the steps of:
 exposing at least a portion of said photoresist to activating radiation;  
 developing said exposed photoresist; and  
 etching said developed photoresist.  
 
     
     
       27. The method of  claim 21 , wherein X includes an aromatic portion selected from the group consisting of thiophenes, naphthoic acid, anthracene, naphthalene, benzene, chalcone, phthalimides, pamoic acid, acridine, azo compounds, dibenzofuran, and derivatives thereof. 
     
     
       28. The method of claim  27    21 , wherein X has a formula selected from the group consisting of 
                 
 
       where R 1  is selected from the group consisting of —H and alkyl groups. 
     
     
       29. The method of  claim 22 , wherein   is selected from the group consisting of acrylics, polyesters, epoxy novolacs, polysaccharides, polyethers, polyimides, and mixtures thereof. 
     
     
       30. The method of  claim 21 , wherein X is present in said polymer at a level of from about 10-60% by weight, based upon the total weight of the polymer taken as 100% by weight. 
     
     
       31. The combination of:
 a substrate having a surface;  
 a cured anti-reflective layer adjacent said substrate surface, said anti-reflective layer being formed from a composition comprising a polymer and trimethylolpropane trivinylether dispersed in a solvent system; and  
 a photoresist layer adjacent said anti-reflective coating composition layer.  
 
     
     
       32. A method of forming a final polymer, said method comprising the step of reacting a starting polymer with a chromophore, wherein:
 said starting polymer includes recurring monomers comprising epoxide rings;    said chromophore is selected from the group consisting of trimellitic anhydride and 4-hydroxybenzoic acid; and    during said reacting step, said epoxide ring opens and said chromophore bonds with the opened ring.    
     
     
       33. The combination of:
   a substrate having a surface;        a cured anti - reflective coating composition layer adjacent said substrate surface, said anti - reflective layer being formed from a composition comprising a polymer and a vinyl ether crosslinking agent dispersed in a solvent system, wherein said polymer is selected from the group consisting of polyesters, epoxy novolacs, polysaccharides, polyethers, polyimides, and mixtures thereof, and wherein said solvent system comprises a solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and mixtures thereof; and        a photoresist layer adjacent said anti - reflective coating composition layer.      
     
     
       34. The combination of  claim 33 , wherein said anti- reflective coating composition layer yields an interlayer test result of less than about  5   %.  
     
     
       35. The combination of:
   a substrate having a surface;        a cured anti - reflective coating composition layer adjacent said substrate surface, said anti - reflective layer being formed from a composition comprising a polymer and a vinyl ether crosslinking agent dispersed in a solvent system, wherein said polymer is selected from the group consisting of polyesters, epoxy novolacs, polysaccharides, polyethers, polyimides, and mixtures thereof; and        a photoresist layer adjacent said anti - reflective coating composition layer, wherein said anti - reflective coating composition layer yields an interlayer test result of less than about  5   %.    
     
     
       36. A method of using an anti- reflective coating composition, said method comprising:      applying a quantity of a composition to a substrate to form an anti - reflective composition layer thereon, said composition comprising a polymer and a vinyl ether crosslinking agent dispersed in a solvent system, wherein said composition yields an interlayer test result of less than  5   %;      applying a quantity of photoresist adjacent to said anti - reflective composition layer to form a photoresist layer thereon;        exposing at least a portion of said photoresist to activating radiation;        developing said exposed photoresist;        etching said photoresist after said developing; and        etching said anti - reflective composition layer.      
     
     
       37. The method of  claim 36 , wherein said solvent system comprises a solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and mixtures thereof.  
     
     
       38. A method of using an anti- reflective coating composition, said method comprising:      applying a quantity of a composition to a substrate to form an anti - reflective composition layer thereon, said composition comprising a polymer and a vinyl ether crosslinking agent dispersed in a solvent system, said solvent system comprising a solvent selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and mixtures thereof; and        applying a quantity of photoresist adjacent to said anti - reflective composition layer to form a layer thereon;        exposing at least a portion of said photoresist to activating radiation;        developing said exposed photoresist;        etching said photoresist after said developing; and        etching said anti - reflective composition layer.      
     
     
       39. A cured anti- reflective layer adjacent a substrate, said antireflective layer comprising a crosslinked polymer including recurring monomers having a formula                      
       
         wherein:  
         
           each R is individually selected from the group consisting of —OH, —H, and alkyl groups;  
         
           X is an aromatic or heterocyclic light - absorbing moiety; and    
         
           at least one of X or R is, or comprises, an —OR 
           2  
           group, where R 
           2  
           is a crosslinking group selected from the group consisting of moieties of trimethylolpropane trivinylether and trimethylolpropane triglycidylether.  
         
       
     
     
       40. The method of  claim 25 , wherein said anti- reflective coating composition yields an interlayer test result of less than about  5   %.