Radiation sensitive resin composition

Abstract

A radiation sensitive resin composition which comprises (A) a polymer which becomes alkali-soluble in the presence of an acid and (B) a radiation sensitive acid generator which generates an acid upon irradiation with a radiation, said polymer (A) comprising two recurring units represented by the general formulas (1) and (2) and a recurring unit which acts to reduce the solubility of the polymer is an alkali developer after the irradiation: wherein R 1 represents a hydrogen atom or a methyl group and R 2 represents a hydrogen atom or a methyl group. Said composition provides a chemically amplified positive resist which can give a fine pattern with a good pattern shape, and said resist is freed from volume shrinkage, peeling failure and adhesive failure, is excellent in dry etching resistance and effectively reacts with various radiations to give a good pattern shape which is excellent in photolithographic process stability, said pattern shape having no thinned portion at the upper part.

What is claimed is:  
     
       1. A radiation sensitive resin composition which consists essentially of (A) a polymer which becomes alkali-soluble in the presence of an acid and (B) a radiation sensitive acid generator which generates an acid upon irradiation with a radiation, said polymer (A) comprising two recurring units A and B represented by the general formulas (1) and (2), respectively, and a recurring unit C which acts to reduce the solubility of the polymer in an alkali developer after the irradiation:                    
       wherein R 1  represents a hydrogen atom or a methyl group and R 2  represents a hydrogen atom or a methyl group, and wherein the recurring unit C is derived from at least one organic compound which is free from any acidic substituent and selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylamide and (meth) arylonitrile. 
     
     
       2. The radiation sensitive resin composition according to claim  1 , wherein the recurring unit represented by the general formula (1) corresponds to at least one monomer selected from the group consisting of vinylphenol and α-isopropenylphenol. 
     
     
       3. The radiation sensitive resin composition according to claim  1 , wherein the recurring unit represented by the general formula (2) corresponds to at least one monomer selected from the group consisting of tert-butyl acrylate and tert-butyl methacrylate. 
     
     
       4. The radiation sensitive resin composition according to claim  1 , wherein the polystyrene-reduced weight-average molecular-weight (Mw) of the polymer (A) is 1,500 to 300,000. 
     
     
       5. The radiation sensitive resin composition according to claim  1 , wherein the polystyrene-reduced weight-average molecular-weight of the polymer (A) is 3,000 to 300,000. 
     
     
       6. The radiation sensitive resin composition according to claim  1 , wherein the ratio of the polystyrene-reduced weight-average molecular-weight (Mw) of the polymer (A) to the polystyrene-reduced number-average molecular-weight (Mn) of the polymer (A) (Mw/Mn) is 1 to 5. 
     
     
       7. The radiation sensitive resin composition according to claim  6 , wherein the ratio (Mw/Mn) is 1.5 to 3.5. 
     
     
       8. The radiation sensitive resin composition according to claim  1 , wherein the proportion of the number of the recurring units represented by the general formula (1) in the polymer (A) is 5 to 75% of the total number of all the recurring units contained in the polymer (A). 
     
     
       9. The radiation sensitive resin composition according to claim  1 , wherein the proportion of the number of the recurring units represented by the general formula (2) in the polymer (A) is 10 to 70% of the total number of all the recurring units contained in the polymer (A). 
     
     
       10. The radiation sensitive resin composition according to claim  1 , wherein the proportion of the number of the recurring units which act to reduce the solubility of the polymer (A) in the alkali developer in the polymer (A) is 0.5 to 50% of the total number of all the recurring units contained in the polymer (A). 
     
     
       11. The radiation sensitive resin composition according to claim  1 , wherein the radiation sensitive acid generator (B) is at least one compound selected from the group consisting of onium salts, halogen-containing compounds, sulfone compounds, sulfonate compounds and quinonediazide compounds. 
     
     
       12. The radiation sensitive resin composition according to claim  1 , wherein the amount of the radiation sensitive acid generator (B) used is 0.05 to 20 parts by weight per 100 parts by weight of the polymer (A). 
     
     
       13. The radiation sensitive resin composition according to claim  1 , wherein the amount of the radiation sensitive acid generator (B) used is 0.1 to 15 parts by weight per 100 parts by weight of the polymer (A). 
     
     
       14. The radiation sensitive resin composition according to claim  1 , which further contains an alkali-solubility controller. 
     
     
       15. The radiation sensitive resin composition according to claim  14 , wherein the alkali-solubility controller is a compound having an acidic functional group which has been substituted by an acid-decomposable group. 
     
     
       16. The radiation sensitive resin composition according to claim  1 , which further contains an acid-diffusion controller. 
     
     
       17. The radiation sensitive resin composition according to claim  16 , wherein the acid-diffusion controller is a nitrogen-containing compound whose basicity is not changed by irradiation or heating. 
     
     
       18. A radiation sensitive resin composition which consists essentially of (A) a polymer which becomes alkali-soluble in the presence of an acid and (B) a radiation sensitive acid generator which generates an acid upon irradiation with a radiation, said polymer (A) comprising two recurring units A and B represented by the general formulas (1) and (2) and a recurring unit C which acts to reduce the solubility of the polymer in an alkali developer after the irradiation:                    
       wherein R 1  represents a hydrogen atom or a methyl group and R 2  represents a hydrogen atom or a methyl group, and wherein the recurring unit C is derived from at least one organic compound which is free from any acidic substituent and selected from the group consisting of hetero atom-containing aromatic vinyl compounds, vinyl ketone compounds and hetero atom-containing alicyclic ring compounds. 
     
     
       19. The radiation sensitive resin composition according to claim  11 , wherein the onium salt is at least one compound selected from the group consisting of diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate. 
     
     
       20. The radiation sensitive resin composition according to claim  1 , wherein the ratio of the polystyrene-reduced weight-average molecular weight (Mw) of the polymer (A) to the polystyrene-reduced number average molecular weight (Mn) of the polymer (A) is 1 to 5. 
     
     
       21. The radiation sensitive resin composition according to claim  1 , which further contains an alkali-solubility controller. 
     
     
       22. The radiation sensitive resin composition according to claim  1 , which further contains an acid-diffusion controller. 
     
     
       23. The radiation sensitive resin composition according to claim  18 , which further contains an alkali-solubility controller. 
     
     
       24. The radiation sensitive resin composition according to claim  18 , which further contains an acid-diffusion controller. 
     
     
       25. A radiation sensitive resin composition which comprises ( A )  a polymer which becomes alkali - soluble in the presence of an acid and  ( B )  a radiation sensitive acid generator which generates an acid upon irradiation with a radiation, said polymer  ( A )  comprising two recurring units A and B represented by the general formulas  (   1   )  and  (   2   ),  respectively, and a recurring unit C which acts to reduce the solubility of the polymer in an alkali developer after the irradiation:                     
         wherein R   1    represents a hydrogen atom or a methyl group and R   2    represents a hydrogen atom or a methyl group, and wherein the recurring unit C is derived from at least one organic compound which is free from any acidic substituent and selected from the group consisting of styrene, alpha - methylstyrene, p - methylstyrene, methyl  ( meth )  acrylate, ethyl  ( meth )  acrylate, propyl  ( meth )  acrylate,  ( meth )  acrylamide and  ( meth )  arylonitrile.   
     
     
       26. The radiation sensitive resin composition according to claim  25 , wherein the recurring unit represented by the general formula (   1   )  corresponds to at least one monomer selected from the group consisting of vinylphenol and alpha - isopropenylphenol.   
     
     
       27. The radiation sensitive resin composition according to claim  25 , wherein the recurring unit represented by the general formula (   2   )  corresponds to at least one monomer selected from the group consisting of tert - butyl acrylate and tert - butyl methacrylate.   
     
     
       28. The radiation sensitive resin composition according to claim  25 , wherein the polystyrene- reduced weight - average molecular - weight  ( Mw )  of the polymer  ( A )  is  1 , 500  to  300 , 000 .   
     
     
       29. The radiation sensitive resin composition according to claim  25 , wherein the polystyrene- reduced weight - average molecular - weight of the polymer  ( A )  is  3 , 000  to  300 , 000 .   
     
     
       30. The radiation sensitive resin composition according to claim  25 , wherein the ratio of the polystyrene- reduced weight - average molecular - weight  ( Mw )  of the polymer  ( A )  to the polystyrene - reduced number - average molecular - weight  ( Mn )  of the polymer  ( A ) ( Mw/Mn )  is  1  to  5 .   
     
     
       31. The radiation sensitive resin composition according to claim  30 , wherein the ratio ( Mw/Mn )  is  1 . 5  to  3 . 5 .   
     
     
       32. The radiation sensitive resin composition according to claim  25 , wherein the proportion of the number of the recurring units represented by the general formula (   1   )  in the polymer  ( A )  is  5  to  75   %  of the total number of all the recurring units contained in the polymer  ( A ). 
     
     
       33. The radiation sensitive resin composition according to claim  25 , wherein the proportion of the number of the recurring units represented by the general formula (   2   )  in the polymer  ( A )  is  10  to  70   %  of the total number of all the recurring units contained in the polymer  ( A ). 
     
     
       34. The radiation sensitive resin composition according to claim  25 , wherein the proportion of the number of the recurring units which act to reduce the solubility of the polymer ( A )  in the alkali developer in the polymer  ( A )  is  0 . 5  to  50   %  of the total number of all the recurring units contained in the polymer  ( A ). 
     
     
       35. The radiation sensitive resin composition according to claim  25 , wherein the radiation sensitive acid generator ( B )  is at least one compound selected from the group consisting of onium salts, halogen - containing compounds, sulfone compounds, sulfonate compounds and quinonediazide compounds.   
     
     
       36. The radiation sensitive resin composition according to claim  25 , wherein the amount of the radiation sensitive acid generator ( B )  used is  0 . 05  to  20  parts by weight per  100  parts by weight of the polymer  ( A ). 
     
     
       37. The radiation sensitive resin composition according to claim  25 , wherein the amount of the radiation sensitive acid generator ( B )  used is  0 . 1  to  15  parts by weight per  100  parts by weight of the polymer  ( A ). 
     
     
       38. The radiation sensitive resin composition according to claim  25 , which further contains an alkali- solubility controller.   
     
     
       39. The radiation sensitive resin composition according to claim  38 , wherein the alkali- solubility controller is a compound having an acidic functional group which has been substituted by an acid - decomposable group.   
     
     
       40. The radiation sensitive resin composition according to claim  25 , which further contains an acid- diffusion controller.   
     
     
       41. The radiation sensitive resin composition according to claim  40 , wherein the acid- diffusion controller is a nitrogen - containing compound whose basicity is not changed by irradiation or heating.   
     
     
       42. A radiation sensitive resin composition which comprises ( A )  a polymer which becomes alkali - soluble in the presence of an acid and  ( B )  a radiation sensitive acid generator which generates an acid upon irradiation with a radiation, said polymer  ( A )  comprising two recurring units A and B represented by the general formulas  (   1   )  and  (   2   )  and a recurring unit C which acts to reduce the solubility of the polymer in an alkali developer after the irradiation:                     
         wherein R   1    represents a hydrogen atom or a methyl group and R   2    represents a hydrogen atom or a methyl group, and wherein the recurring unit C is derived from at least one organic compound which is free from any acidic substituent and selected from the group consisting of hetero atom - containing aromatic vinyl compounds, vinyl ketone compounds and hetero atom - containing alicyclic ring compounds.   
     
     
       43. The radiation sensitive resin composition according to claim  35 , wherein the onium salt is at least one compound selected from the group consisting of diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, ( hydroxyphenyl ) benzylmethylsulfonium toluenesulfonate.   
     
     
       44. The radiation sensitive resin composition according to claim  25 , wherein the ratio of the polystyrene- reduced weight - average molecular weight  ( Mw )  of the polymer  ( A )  to the polystyrene - reduced number average molecular weight  ( Mn )  of the polymer  ( A )  is  1  to  5 .   
     
     
       45. The radiation sensitive resin composition according to claim  25 , which further contains an alkali- solubility controller.   
     
     
       46. The radiation sensitive resin composition according to claim  25 , which further contains an acid- diffusion controller.   
     
     
       47. The radiation sensitive resin composition according to claim  42 , which further contains an alkali- solubility controller.   
     
     
       48. The radiation sensitive resin composition according to claim  42 , which further contains an acid- diffusion controller.   
     
     
       49. The composition of claim  1 , wherein said composition further consists essentially of a solvent. 
     
     
       50. The composition of claim  49 , wherein said composition further consists essentially of a surfactant. 
     
     
       51. The composition of claim  49 , wherein said composition further consists essentially of a sensitizer. 
     
     
       52. The composition of claim  51 , wherein said sensitizer is added in amount of no more than fifty parts by weight, per one hundred parts by weight of solid content of said radiation sensitive resin composition. 
     
     
       53. The composition of claim  50 , wherein said surfactant is present in amounts of no more than two parts by weight per one hundred parts by weight of solid content of said radiation sensitive resin composition. 
     
     
       54. The composition of claim  49 , wherein said composition further consists essentially of a dye or pigment. 
     
     
       55. The composition of claim  49 , wherein said composition further consists essentially of an adhesion promoter. 
     
     
       56. The composition of claim  49 , wherein said composition further consists essentially of at least one additive selected from the group consisting of a halation- preventing agent, a storage stabilizer, a defoaming agent and a shape - improving agent.   
     
     
       57. The composition of claim  49 , wherein said solvent comprises ethyl lactate.