Composition for forming photocurable silicon-containing coating film

Abstract

A photocurable silicon-containing coating film-forming composition including a hydrolyzable silane, a hydrolysate thereof, or a hydrolytic condensate thereof, wherein the hydrolyzable silane includes a hydrolyzable silane of the following Formula (1): R 1 a R 2 b Si(R 3 ) 4-(a+b)   Formula (1) (wherein R 1 is a functional group relating to photocrosslinking). The photocurable silicon-containing coating film-forming composition, wherein the composition may be for forming a silicon-containing coating film that may be cured by ultraviolet irradiation and may serve as an intermediate layer between a resist film and an organic underlayer film on a substrate in a lithographic process for producing a semiconductor device.

1 . A photocurable silicon-containing coating film-forming composition comprising a hydrolyzable silane, a hydrolysate thereof, or a hydrolytic condensate thereof, wherein the hydrolyzable silane is a hydrolyzable silane of the following Formula (1):
   R 1   a R 2   b Si(R 3 ) 4-(a+b)   Formula (1)
   (wherein R 1  is an organic group (1) having a multiple bond between a carbon atom and a carbon atom, an oxygen atom, or a nitrogen atom, an epoxide-containing organic group (2), a sulfur-containing organic group (3), an organic group (4) containing an amide group, a primary to tertiary amino group, or a primary to tertiary ammonium group, a phenoplast-forming group (5) containing a phenolic-group-containing organic group or a phenolic-group-generating organic group and a methylol-group-containing organic group or a methylol-group-generating organic group, or an organic group containing any combination of these groups, and is bonded to a silicon atom via an Si—C bond; R 2  is an alkyl group and is bonded to a silicon atom via an Si—C bond; R 3  is an alkoxy group, an acyloxy group, or a halogen group; a is an integer of 1; b is an integer of 0 to 2; and a+b is an integer of 1 to 3).   
     
     
         2 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the hydrolyzable silane contains a hydrolyzable silane of Formula (1) and at least one hydrolyzable silane selected from the group consisting of a hydrolyzable silane of the following Formula (2):
   R 4   c Si(R 5 ) 4-c   Formula (2)
   (wherein R 4  is an alkyl group or an aryl group and is bonded to a silicon atom via an Si—C bond; R 5  is an alkoxy group, an acyloxy group, or a halogen group; and c is an integer of 0 to 3) and a hydrolyzable silane of the following Formula (3):
     R 6   d Si(R 7 ) 3-d     2 Y e   Formula (3)
 
   (wherein R 6  is an alkyl group or an aryl group and is bonded to a silicon atom via an Si—C bond; R 7  is an alkoxy group, an acyloxy group, or a halogen group; Y is an alkylene group or an arylene group; d is an integer of 0 or 1; and e is an integer of 0 or 1).   
     
     
         3 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the organic group (1) having a multiple bond between a carbon atom and a carbon atom is a vinyl group, a propargyl group, an allyl group, an acryloyl group, a methacryloyl group, a styryl group, a substituted phenyl group, a norbornene group, or an organic group containing any of these groups. 
     
     
         4 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the organic group (1) having a multiple bond between a carbon atom and an oxygen atom is a carbonyl group, an acyl group, or an organic group containing any of these groups. 
     
     
         5 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the organic group (1) having a multiple bond between a carbon atom and a nitrogen atom is a nitrile group, an isocyanate group, or an organic group containing any of these groups. 
     
     
         6 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the epoxide-containing organic group (2) is an epoxy group, a cyclohexylepoxy group, a glycidyl group, an oxetanyl group, or a dihydroxyalkyl group formed by ring opening of any of these groups, or an organic group containing any of these groups. 
     
     
         7 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the sulfur-containing organic group (3) is a thiol group, a sulfide group, a disulfide group, or an organic group containing any of these groups. 
     
     
         8 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the organic group (4) containing an amide group is a sulfonamide group, a carboxylic acid amide group, or an organic group containing any of these groups. 
     
     
         9 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the organic group (4) containing a primary to tertiary ammonium group is a group formed by bonding between an organic group containing a primary to tertiary amino group and an acid. 
     
     
         10 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the phenoplast-forming group (5) is an acetalized phenyl group, an alkoxybenzyl group, or an organic group containing any of these groups. 
     
     
         11 . The photocurable silicon-containing coating film-forming composition according to  claim 1 , wherein the composition is a photocurable silicon-containing resist underlayer film-forming composition for forming a silicon-containing resist underlayer film that is cured by ultraviolet irradiation and serves as an intermediate layer between a resist film and an organic underlayer film on a substrate in a lithographic process for producing a semiconductor device. 
     
     
         12 . A method for producing a coated substrate, the method comprising a step (i) of applying the photocurable silicon-containing coating film-forming composition according to  claim 1  to an uneven substrate; and a step (ii) of exposing the photocurable silicon-containing coating film-forming composition to light. 
     
     
         13 . The method for producing a coated substrate according to  claim 12 , wherein the method further comprises a step (ia) of heating the photocurable silicon-containing coating film-forming composition at a temperature of 70 to 400° C. for 10 seconds to five minutes after application of the composition to the uneven substrate in the step (i). 
     
     
         14 . The method for producing a coated substrate according to  claim 12 , wherein light used for the light exposure in the step (ii) has a wavelength of 150 nm to 330 nm. 
     
     
         15 . The method for producing a coated substrate according to  claim 12 , wherein the dose of exposure light in the step (ii) is 10 mJ/cm 2  to 3,000 mJ/cm 2 . 
     
     
         16 . The method for producing a coated substrate according to  claim 12 , wherein the light exposure in the step (ii) is performed in an inert gas atmosphere containing oxygen and/or water vapor. 
     
     
         17 . The method for producing a coated substrate according to  claim 12 , wherein the substrate has an open area (non-patterned area) and a patterned area of DENSE (dense) and ISO (coarse), and the pattern has an aspect ratio of 0.1 to 10. 
     
     
         18 . The method for producing a coated substrate according to  claim 12 , wherein the substrate has an open area (non-patterned area) and a patterned area of DENSE (dense) and ISO (coarse), and the difference in coating level (Bias) between the open area and the patterned area is 1 to 50 nm. 
     
     
         19 . A method for producing a semiconductor device, the method comprising a step of forming, on an uneven substrate, a resist underlayer film from the photocurable silicon-containing coating film-forming composition according to  claim 1 ; a step of forming a resist film on the resist underlayer film; a step of irradiating the resist film with light or electron beams and developing the resist film, to thereby form a resist pattern; a step of etching the resist underlayer film with the resist pattern; and a step of processing a semiconductor substrate with the patterned resist underlayer film. 
     
     
         20 . The method for producing a semiconductor device according to  claim 19 , wherein the uneven substrate has an open area (non-patterned area) and a patterned area of DENSE (dense) and ISO (coarse), and the pattern has an aspect ratio of 0.1 to 10. 
     
     
         21 . A method for producing a semiconductor device, the method comprising a step of forming, on an uneven substrate, a resist underlayer film from a photocurable silicon-containing coating film-forming composition comprising a hydrolyzable silane, a hydrolysate thereof, or a hydrolytic condensate thereof, wherein the hydrolyzable silane is a hydrolyzable silane of the following Formula (1):
   R 1   a R 2   b Si(R 3 ) 4-(a+b)   Formula (1)
   (wherein R 1  is an organic group (1) having a multiple bond between a carbon atom and a carbon atom, an oxygen atom, or a nitrogen atom, an epoxide-containing organic group (2), a sulfur-containing organic group (3), an organic group (4) containing an amide group, a primary to tertiary amino group, or a primary to tertiary ammonium group, a phenoplast-forming group (5) containing a phenolic-group-containing organic group or a phenolic-group-generating organic group and a methylol-group-containing organic group or a methylol-group-generating organic group, or an organic group containing any combination of these groups, and is bonded to a silicon atom via an Si—C bond; R 2  is an alkyl group and is bonded to a silicon atom via an Si—C bond; R 3  is an alkoxy group, an acyloxy group, or a halogen group; a is an integer of 1; b is an integer of 0 to 2; and a+b is an integer of 1 to 3);   a step of forming a resist film on the resist underlayer film; a step of irradiating the resist film with light or electron beams and developing the resist film, to thereby form a resist pattern; a step of etching the resist underlayer film with the resist pattern; and a step of processing a semiconductor substrate with the patterned resist underlayer film,   wherein the step of forming a resist underlayer film from the photocurable silicon-containing coating film-forming composition is a step of forming the resist underlayer film by the method according to  claim 12 .   
     
     
         22 . The method for producing a semiconductor device according to  claim 21 , wherein the uneven substrate has an open area (non-patterned area) and a patterned area of DENSE (dense) and ISO (coarse), and the pattern has an aspect ratio of 0.1 to 10. 
     
     
         23 . The method for producing a semiconductor device according to  claim 19 , wherein the resist underlayer film formed from the photocurable silicon-containing coating film-forming composition has the difference in coating level (Bias) between the open area and the patterned area is 1 to 50 nm. 
     
     
         24 . A method for producing a semiconductor device, the method comprising a step of forming, on an uneven substrate, an organic underlayer film from a photocurable organic underlayer film-forming composition; a step of forming, on the organic underlayer film, a resist underlayer film from the photocurable silicon-containing coating film-forming composition according to  claim 1 ; a step of forming a resist film on the resist underlayer film; a step of irradiating the resist film with light or electron beams and developing the resist film, to thereby form a resist pattern; a step of etching the resist underlayer film with the resist pattern; a step of etching the organic underlayer film with the patterned resist underlayer film; and a step of processing a semiconductor substrate with the patterned organic underlayer film. 
     
     
         25 . A method for producing a semiconductor device, the method comprising a step of forming, on an uneven substrate, an organic underlayer film from a photocurable organic underlayer film-forming composition; a step of forming, on the organic underlayer film, a resist underlayer film from a photocurable silicon-containing coating film-forming composition comprising a hydrolyzable silane, a hydrolysate thereof, or a hydrolytic condensate thereof, wherein the hydrolyzable silane is a hydrolyzable silane of the following Formula (1):
   R 1   a R 2   b Si(R 3 ) 4-(a+b)   Formula (1)
   (wherein R 1  is an organic group (1) having a multiple bond between a carbon atom and a carbon atom, an oxygen atom, or a nitrogen atom, an epoxide-containing organic group (2), a sulfur-containing organic group (3), an organic group (4) containing an amide group, a primary to tertiary amino group, or a primary to tertiary ammonium group, a phenoplast-forming group (5) containing a phenolic-group-containing organic group or a phenolic-group-generating organic group and a methylol-group-containing organic group or a methylol-group-generating organic group, or an organic group containing any combination of these groups, and is bonded to a silicon atom via an Si—C bond; R 2  is an alkyl group and is bonded to a silicon atom via an Si—C bond; R 3  is an alkoxy group, an acyloxy group, or a halogen group; a is an integer of 1; b is an integer of 0 to 2; and a+b is an integer of 1 to 3);   a step of forming a resist film on the resist underlayer film; a step of irradiating the resist film with light or electron beams and developing the resist film, to thereby form a resist pattern; a step of etching the resist underlayer film with the resist pattern; a step of etching the organic underlayer film with the patterned resist underlayer film; and a step of processing a semiconductor substrate with the patterned organic underlayer film,   wherein the step of forming a resist underlayer film from the photocurable silicon-containing coating film-forming composition is a step of forming the resist underlayer film by the method according to  claim 12 .   
     
     
         26 . The method for producing a semiconductor device according to  claim 24 , wherein the resist underlayer film formed from the photocurable silicon-containing coating film-forming composition has the difference in coating level (Bias) between the open area and the patterned area is 1 to 50 nm.