Material for forming underlayer film, resist underlayer film, method of producing resist underlayer film, and laminate

Abstract

A material for forming an underlayer film according to the present invention is a material for forming an underlayer film which is used to form a resist underlayer film used in a multi-layer resist process, the material including a cyclic olefin polymer which has a repeating structural unit [A] represented by Formula (1) and a repeating structural unit [B] represented by Formula (2), in which a molar ratio [A]/[B] of the structural unit [A] to the structural unit [B] in the cyclic olefin polymer is greater than or equal to 5/95 and less than or equal to 95/5.

1 . A material for forming an underlayer film which is used to form a resist underlayer film used in a multi-layer resist process, the material comprising:
 a cyclic olefin polymer which has a repeating structural unit [A] represented by Formula (1) and a repeating structural unit [B] represented by Formula (2),   wherein a molar ratio [A]/[B] of the structural unit [A] to the structural unit [B] in the cyclic olefin polymer is greater than or equal to 5/95 and less than or equal to 95/5.   
       
         
           
           
               
               
           
         
         (in Formula (1), at least one of R 1  to R 4  is selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an aryloxyalkyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a dialkylaminocarbonyl group having 3 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkylarylaminocarbonyl group having 8 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 30 carbon atoms, an alkoxycarbonylaryl group having 8 to 30 carbon atoms, an aryloxycarbonylalkyl group having 8 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, and an alkoxycarbonylalkyloxycarbonyl group having 4 to 30 carbon atoms, R 1  to R 4  may be bonded to one another to form a ring structure, and n represents an integer of 0 to 2), and 
       
       
         
           
           
               
               
           
         
         (in Formula (2), at least one of R 5  to R 8  is selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an aryloxyalkyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a dialkylaminocarbonyl group having 3 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkylarylaminocarbonyl group having 8 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 30 carbon atoms, an alkoxycarbonylaryl group having 8 to 30 carbon atoms, an aryloxycarbonylalkyl group having 8 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, and an alkoxycarbonylalkyloxycarbonyl group having 4 to 30 carbon atoms, R 5  to R 8  may be bonded to one another to form a ring structure, n represents an integer of 0 to 2, and X 1  represents —O— or —S—) 
       
     
     
         2 . The material for forming an underlayer film according to  claim 1 ,
 wherein a temperature showing an intersection between a storage modulus (G′) curve and a loss modulus (G″) curve in a solid viscoelasticity of the cyclic olefin polymer which are measured under conditions of a measurement temperature range of 30° C. to 300° C., a heating rate of 3° C./min, and a frequency of 1 Hz in a nitrogen atmosphere in a shear mode using a rheometer is higher than or equal to 40° C. and lower than or equal to 200° C.   
     
     
         3 . The material for forming an underlayer film according to  claim 1 ,
 wherein a temperature showing an intersection between a storage modulus (G′) curve and a loss modulus (G″) curve in a solid viscoelasticity of the material for forming an underlayer film which is measured under conditions of a measurement temperature range of 30° C. to 300° C., a heating rate of 3° C./min, and a frequency of 1 Hz in a nitrogen atmosphere in a shear mode using a rheometer is higher than or equal to 40° C. and lower than or equal to 200° C.   
     
     
         4 . The material for forming an underlayer film according to  claim 2 ,
 wherein the temperature showing the intersection between the storage modulus (G′) curve and the loss modulus (G″) curve in the solid viscoelasticity is higher than or equal to 80° C. and lower than or equal to 200° C.   
     
     
         5 . The material for forming an underlayer film according to  claim 1 ,
 wherein an amount of a volatile component in the cyclic olefin polymer which is measured using the following method 1 is greater than or equal to 0.0% by mass to 1.0% by mass in a case where a total amount of the cyclic olefin polymer is set to 100% by mass.   (method 1: the cyclic olefin polymer is dissolved in tetrahydrofuran to prepare a solution having a solid content concentration of 20% by mass, the obtained solution is weighed using an aluminum plate, heated at 200° C. for 3 minutes in a nitrogen flow such that the tetrahydrofuran is removed, and cooled to room temperature such that the cyclic olefin polymer is solidified, the cyclic olefin polymer is heated in a temperature range of 30° C. to 300° C. at a heating rate of 10° C./min in a nitrogen atmosphere, and the amount of the volatile component in the cyclic olefin polymer is calculated based on a weight reduction amount in a temperature range of 100° C. to 250° C.)   
     
     
         6 . The material for forming an underlayer film according to  claim 1 ,
 wherein a weight-average molecular weight (Mw) of the cyclic olefin polymer in terms of polystyrene which is measured using gel permeation chromatography is greater than or equal to 1000 and less than or equal to 20000.   
     
     
         7 . The material for forming an underlayer film according to  claim 1 ,
 wherein a refractive index (n value) of the cyclic olefin polymer at a wavelength of 193 nm which is measured using the following method 2 is greater than or equal to 1.5 and less than or equal to 2.0.   (method 2: a coating film which is formed of the cyclic olefin polymer and has a thickness of 250 nm is formed on a silicon wafer, and the refractive index (n value) of the obtained coating film at a wavelength of 193 nm is set as the refractive index (n value) of the cyclic olefin polymer)   
     
     
         8 . The material for forming an underlayer film according to  claim 1 ,
 wherein a refractive index (n value) of the material for forming an underlayer film at a wavelength of 193 nm which is measured using the following method 2 is greater than or equal to 1.5 and less than or equal to 2.0.   (method 2: a coating film which is formed of the material for forming an underlayer film and has a thickness of 250 nm is formed on a silicon wafer, and the refractive index (n value) of the obtained coating film at a wavelength of 193 nm is set as the refractive index (n value) of the material for forming an underlayer film)   
     
     
         9 . The material for forming an underlayer film according to  claim 1 ,
 wherein an extinction coefficient (k value) of the cyclic olefin polymer which is measured using the following method 3 is greater than or equal to 0.0001 and less than or equal to 0.5.   (method 3: a coating film which is formed of the cyclic olefin polymer and has a thickness of 250 nm is formed on a silicon wafer, and the extinction coefficient (k value) of the obtained coating film is set as the extinction coefficient (k value) of the cyclic olefin polymer)   
     
     
         10 . The material for forming an underlayer film according to  claim 1 ,
 wherein an extinction coefficient (k value) of the material for forming an underlayer film which is measured using the following method 3 is greater than or equal to 0.0001 and less than or equal to 0.5.   (method 3: a coating film which is formed of the material for forming an underlayer film and has a thickness of 250 nm is formed on a silicon wafer, and the extinction coefficient (k value) of the obtained coating film is set as the extinction coefficient (k value) of the material for forming an underlayer film)   
     
     
         11 . The material for forming an underlayer film according to  claim 1 ,
 which is formed on an uneven structure of a substrate having the uneven structure and is used for an underlayer film for embedding a recess in the uneven structure.   
     
     
         12 . The material for forming an underlayer film according to  claim 1 ,
 wherein a content of a crosslinking agent in the material for forming an underlayer film is less than 5 parts by mass in a case where a total content of polymer components contained in the material for forming an underlayer film is set to 100 parts by mass.   
     
     
         13 . The material for forming an underlayer film according to  claim 1 ,
 wherein a content of the cyclic olefin polymer in the material for forming an underlayer film is greater than or equal to 50% by mass and less than or equal to 100% by mass in a case where a total content of the material for forming an underlayer film is set to 100% by mass.   
     
     
         14 . A material for forming an underlayer film which is used to form a resist underlayer film used in a multi-layer resist process,
 wherein the material for forming an underlayer film is a material of a film containing a cyclic olefin polymer,   the cyclic olefin polymer is soluble in an organic solvent at any concentration of at least greater than or equal to 0.01% by mass and less than or equal to 50% by mass, and   a residual film rate of the cyclic olefin polymer in the film which is measured using the following method 4 is greater than or equal to 50% and less than or equal to 100%.   (method 4: a coating film which is formed of the cyclic olefin polymer and has a thickness (α) of greater than or equal to 200 nm and less than or equal to 500 nm is formed on a silicon wafer, the obtained coating film is treated at 200° C. for 10 minutes, immersed in propylene glycol-1-monomethyl ether-2-acetate at 23° C. for 10 minutes, and dried under conditions of 150° C. for 3 minutes, and a remaining solvent in the coating film is removed, and a thickness (β) of the coating film obtained by removing the remaining solvent is measured, and the residual film rate (=β/α×100) (%) is calculated)   
     
     
         15 . A material for forming an underlayer film which is used to form a resist underlayer film used in a multi-layer resist process, the material comprising:
 a cyclic olefin polymer,   wherein a residual film rate of the material for forming an underlayer film which is measured using the following method 4 is greater than or equal to 50% and less than or equal to 100%.   (method 4: a coating film which is formed of the material for forming an underlayer film and has a thickness (α) of greater than or equal to 200 nm and less than or equal to 500 nm is formed on a silicon wafer, the obtained coating film is treated at 200° C. for 10 minutes, immersed in propylene glycol-1-monomethyl ether-2-acetate at 23° C. for 10 minutes, and dried under conditions of 150° C. for 3 minutes, and a remaining solvent in the coating film is removed, and a thickness (β) of the coating film obtained by removing the remaining solvent is measured, and the residual film rate (=β/α×100) (%) is calculated)   
     
     
         16 . The material for forming an underlayer film according to  claim 14 ,
 wherein the cyclic olefin polymer has a repeating structural unit [A] represented by Formula (1) and a repeating structural unit [B] represented by Formula (2),   a molar ratio [A]/[B] of the structural unit [A] to the structural unit [B] in the cyclic olefin polymer is greater than or equal to 5/95 and less than or equal to 95/5.   
       
         
           
           
               
               
           
         
         (in Formula (1), at least one of R 1  to R 4  is selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an aryloxyalkyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a dialkylaminocarbonyl group having 3 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkylarylaminocarbonyl group having 8 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 30 carbon atoms, an alkoxycarbonylaryl group having 8 to 30 carbon atoms, an aryloxycarbonylalkyl group having 8 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, and an alkoxycarbonylalkyloxycarbonyl group having 4 to 30 carbon atoms, R 1  to R 4  may be bonded to one another to form a ring structure, and n represents an integer of 0 to 2), and 
       
       
         
           
           
               
               
           
         
         (in Formula (2), at least one of R 5  to R 8  is selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an aryloxyalkyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a dialkylaminocarbonyl group having 3 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkylarylaminocarbonyl group having 8 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 30 carbon atoms, an alkoxycarbonylaryl group having 8 to 30 carbon atoms, an aryloxycarbonylalkyl group having 8 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, and an alkoxycarbonylalkyloxycarbonyl group having 4 to 30 carbon atoms, R 5  to R 8  may be bonded to one another to form a ring structure, n represents an integer of 0 to 2, and X 1  represents —O— or —S—) 
       
     
     
         17 . The material for forming an underlayer film according to  claim 14 ,
 wherein a weight-average molecular weight (Mw) of the cyclic olefin polymer in terms of polystyrene which is measured using gel permeation chromatography is greater than or equal to 1000 and less than or equal to 20000.   
     
     
         18 . The material for forming an underlayer film according to  claim 14 ,
 wherein a refractive index (n value) of the cyclic olefin polymer at a wavelength of 193 nm which is measured using the following method 2 is greater than or equal to 1.5 and less than or equal to 2.0.   (method 2: a coating film which is formed of the cyclic olefin polymer and has a thickness of 250 nm is formed on a silicon wafer, and the refractive index (n value) of the obtained coating film at a wavelength of 193 nm is set as the refractive index (n value) of the cyclic olefin polymer)   
     
     
         19 . The material for forming an underlayer film according to  claim 14 ,
 wherein a refractive index (n value) of the material for forming an underlayer film at a wavelength of 193 nm which is measured using the following method 2 is greater than or equal to 1.5 and less than or equal to 2.0.   (method 2: a coating film which is formed of the material for forming an underlayer film and has a thickness of 250 nm is formed on a silicon wafer, and the refractive index (n value) of the obtained coating film at a wavelength of 193 nm is set as the refractive index (n value) of the material for forming an underlayer film)   
     
     
         20 . The material for forming an underlayer film according to  claim 14 ,
 wherein an extinction coefficient (k value) of the cyclic olefin polymer which is measured using the following method 3 is greater than or equal to 0.0001 and less than or equal to 0.5.   (method 3: a coating film which is formed of the cyclic olefin polymer and has a thickness of 250 nm is formed on a silicon wafer, and the extinction coefficient (k value) of the obtained coating film is set as the extinction coefficient (k value) of the cyclic olefin polymer)   
     
     
         21 . The material for forming an underlayer film according to  claim 14 ,
 wherein an extinction coefficient (k value) of the material for forming an underlayer film which is measured using the following method 3 is greater than or equal to 0.0001 and less than or equal to 0.5.   (method 3: a coating film which is formed of the material for forming an underlayer film and has a thickness of 250 nm is formed on a silicon wafer, and the extinction coefficient (k value) of the obtained coating film is set as the extinction coefficient (k value) of the material for forming an underlayer film)   
     
     
         22 . The material for forming an underlayer film according to  claim 14 ,
 which is formed on an uneven structure of a substrate having the uneven structure and is used for an underlayer film for embedding a recess in the uneven structure.   
     
     
         23 . The material for forming an underlayer film according  claim 14 ,
 wherein a content of a crosslinking agent in the material for forming an underlayer film is less than 5 parts by mass in a case where a total content of polymer components contained in the material for forming an underlayer film is set to 100 parts by mass.   
     
     
         24 . The material for forming an underlayer film according to  claim 14 ,
 wherein a content of the cyclic olefin polymer in the material for forming an underlayer film is greater than or equal to 50% by mass and less than or equal to 100% by mass in a case where a total content of the material for forming an underlayer film is set to 100% by mass.   
     
     
         25 . A resist underlayer film comprising:
 the material for forming an underlayer film according to  claim 1 .   
     
     
         26 . A method of producing a resist underlayer film, comprising:
 a step of forming a coating film which contains the material for forming an underlayer film according to  claim 1  on a substrate.   
     
     
         27 . The method of producing a resist underlayer film according to  claim 26 , further comprising:
 heating the coating film.   
     
     
         28 . A laminate comprising:
 a substrate; and   a resist underlayer film containing the material for forming an underlayer film according to  claim 1 , which is formed on one surface of the substrate.   
     
     
         29 . The laminate according to  claim 28 ,
 wherein a flatness ΔFT of a surface (α) of the resist underlayer film on a side opposite to the substrate which is calculated using the following equation is greater than or equal to 0% and less than or equal to 5%.
   flatness (Δ FT )=[( H   max   −H   min )/ H   av ]×100(%)
 
   (where film thicknesses of the resist underlayer film are measured in ten optional sites of the surface (α), an average value of these measured values is set as Hav, a maximum value in the film thicknesses of the resist underlayer film is set as H max , and a minimum value in the film thicknesses of the resist underlayer film is set as H min )   
     
     
         30 . The laminate according to  claim 28 ,
 wherein an average value Hav of the film thickness of the resist underlayer film is greater than or equal to 5 nm and less than or equal to 1000 nm.   (where film thicknesses of the resist underlayer film are measured in ten optional sites of the surface (α) of the resist underlayer film on the side opposite to the substrate, and the average value of these measured values is set as Hav)   
     
     
         31 . The laminate according to  claim 28 ,
 wherein the substrate has an uneven structure on at least one surface thereof,   the resist underlayer film is formed on the uneven structure,   the uneven structure has a height of greater than or equal to 5 nm and less than or equal to 500 nm, and   an interval between projections is greater than or equal to 1 nm and less than or equal to 10 mm.