Composition for resist underlayer film and method for producing the same

A composition for a resist underlayer film comprising:

• both or either of a hydrolysate and a condensate of (A) at least one compound selected from the group consisting of (A-1) a compound represented by the following general formula (1):
• R1aSi (OR2) 4-a (1)
• wherein R1 represents a hydrogen atom, a fluorine atom or a univalent organic group, R2 represents a univalent organic group, and a represents an integer of 0 to 2, and (A-2) a compound represented by the following general formula (2):
• R3b(R4O)3-bSi-(R7)d-Si(OR5)3-cR6c (2)
• wherein R3, R4, R5 and R6, which may be the same or different, each represent univalent organic groups, b and c, which may by the same or different, each represent integers of 0 to 2, R7 represents an oxygen atom or -(CH2)n-, d represents 0 or 1, and n represents an interger of 1to 6, and
• (B) a compound generating an acid by ultraviolet irradiation and/or heating;
• in which composition (A) is both or either of a hydrolysate and a condensate of (a1) a compound represented by the following general formula (3):
• Si(OR2)4 (3)
• wherein R2 represents a univalent organic group.

A method for producing a composition for a resist underlayer film comprising adding water to (A) at least one compound selected from the group consisting of (A-1) a compound represented by the following general formula (1):

• R1aSi(OR2)4−a (1)
• wherein R1 represents a hydrogen atom, a fluorine atom or a univalent organic group, R2 represents a univalent organic group, and a represents an integer of 0 to 2, and (A-2) a compound represented by the following general formula (2):
• R3b(R4O)3−bSi—(R7)d—Si(OR5)3−cR6c (2)
• wherein R3, R4, R5 and R6, which may be the same or different, each represent univalent organic groups, b and c, which may be the same or different, each represent integers of 0 to 2, R7 represents an oxygen atom or —(CH2)n—, d represents 0 or 1, and n represents an integer of 1 to 6, in an amount of 0.25 mole to 3 moles per mole of the total of alkoxyl groups of the compound represented by general formula (1) and alkoxyl groups of the compound represented by general formula (2), hydrolyzing and/or condensing said compound, wherein neither the compound of general formula (1) nor the compound of general formula (2) contains a glycidyl group, and then adding (B) a compound generating an acid by ultraviolet irradiation and/or heating,
• wherein a resist underlayer film made with said composition changes 1 nm or less in thickness when immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute.

A method for producing a composition for a resist underlayer film comprising adding water to (A) at least one compound selected from the group consisting of (A-1) a compound represented by the following general formula (1):

• R1aSi(OR2)4−a (1)
• wherein R1 represents a hydrogen atom, a fluorine atom or a univalent organic group, R2 represents a univalent organic group, and a represents an integer of 0 to 2, and (A-2) a compound represented by the following general formula (2):
• R9b(R4O)3−bSi—(R7)d—Si(OR5)3−cR6c (2)
• wherein R3, R4, R5 and R6, which may be the same or different, each represent univalent organic groups, b and c, which may be the same or different, each represent integers of 0 to 2, R7 represents an oxygen atom or —(CH2)n—, d represents 0 or 1, and n represents an integer of 1 to 6, in an amount of 0.25 mole to 3 moles per mole of the total of alkoxyl groups of the compound represented by general formula (1) and alkoxyl groups of the compound represented by general formula (2), hydrolyzing and/or condensing said compound, and then adding (B) a compound generating an acid by ultraviolet irradiation and/or heating, in which both or either of a hydrolysate and a condensate of (a1) a compound represented by the following general formula (3):
• Si(OR2)4 (3)
• wherein R2 represents a univalent organic group;
• and both or either of a hydrolysate and a condensate obtained from mixing a compound (a1) and (a2) a compound represented by the following general formula (4):
• R1nSi(OR2)4−n (4)
• wherein R1 and R2, which may be the same or different, each represent univalent organic groups, and n represents an integer of 1 to 3, followed by hydrolysis and condensation of the mixture;
• are mixed with each other to use them as said component (A).

A method for producing a composition for a resist underlayer film comprising adding water to (A) at least one compound selected from the group consisting of (A-1) a compound represented by the following general formula (1):

• R1aSi(OR2)4−a (1)
• wherein R1 represents a hydrogen atom, a fluorine atom or a univalent organic group, R2 represents a univalent organic group, and a represents an integer of 0 to 2, and (A-2) a compound represented by the following general formula (2):
• R3b(R4O)3−bSi—(R7)d—Si(OR5)3−cR6c (2)
• wherein R3, R4, R5 and R6, which may be the same or different, each represent univalent organic groups, b and c, which may be the same or different, each represent integers of 0 to 2, R7 represents an oxygen atom or —(CH2)n—, d represents 0 or 1, and n represents an integer of 1 to 6, in an amount of 0.25 mole to 3 moles per mole of the total of alkoxyl groups of the compound represented by general formula (1) and alkoxyl groups of the compound represented by general formula (2), hydrolyzing and/or condensing said compound, and then adding (B) a compound generating an acid by ultraviolet irradiation and/or heating, in which both or either of a hydrolysate and a condensate of (a1) a compound represented by the following general formula (3):
• Si(OR2)4 (3)
• wherein R2 represents a univalent organic group or either of a hydrolysate and a condensate obtained from mixing a compound (a1) and (a2) a compound represented by the following general formula (4):
• R1nSi(OR2)4-n (4)
• wherein R1 and R2, which may be the same of different, each represent univalent organic groups, and n represents an interger of 1 to 3, followed by hydrolysis and condensation of the mixture;
• are mixed with each other to use them as said component (A).

A method for producing a composition for a resist underlayer film comprising adding water to (A) at least one compound selected from the group consisting of (A-1) a compound represented by the following general formula (1):

• R1aSi(OR2)4−a (1)
• wherein R1 represents a hydrogen atom, a fluorine atom or a univalent organic group, R2 represents a univalent organic group, and a represents an integer of 0 to 2, and (A-2) a compound represented by the following general formula (2):
• R3b(R4O)3−bSi—(R7)d—Si(OR5)3−cR6c (2)
• wherein R3, R4, R5 and R6, which may be the same or different, each represent univalent organic groups, b and c, which may be the same or different, each represent integers of 0 to 2, R7 represents an oxygen atom or —(CH2)n—, d represents 0 or 1, and n represents an integer of 1 to 6, in an amount of 0.25 mole to 3 moles per mole of the total of alkoxyl groups of the compound represented by general formula (1) and alkoxyl groups of the compound represented by general formula (2), hydrolyzing and/or condensing said compound, wherein when any of R1-R6 is a univalent organic group, said univalent organic group is selected from the group consisting of alkyl, aryl and allyl, optionally substituted with halogen or amino, and then adding (B) a compound generating an acid by ultraviolet irradiation and/or heating,
• wherein a resist underlayer film made with said composition changes 1 nm or less in thickness when immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute.

A resist underlayer film obtained by a method comprising adding water to (A) at least one compound selected from the group consisting of (A−1) a compound represented by the following formula (1):

• R1aSi(OR2)4−a (1)
• wherein R1 represents a hydrogen atom, a flourine atom or a univalent organic group, R2 represents a univalent organic group, and a represents an integer of 0 to 2, and (A−2) a compound represented by the following general formula (2):
• R3b(R4O)3−bSi-(R7)d-Si(OR5)3−cR6c (2)
• wherein R3, R4, R5 and R6, which may be the same or different, eacg represent univalent organic groups, b and c, which may be the same or different, each represent integers og 0 to 2, R7 represents an oxygen atom or -(CH2)n-, d represents 0 to 1, and n represents an integer of 1 to 6 , in an amount of 0.25 mole to about 3 moles per mole of the total of alkoxyl groups of the compound represented by the general formula (1) and alkoxyl groups of the compound represented by the general formula (2), hydrolyzing and/or condensing said compound, wherein neither the compound of general formula (1) nor the compound of general formula (2) contains a glycidyl group, and then adding (B) a compound generating an acid by ultraviolet irradiation and/or heating, wherein (A) and (B) are dissolved or dispersed in an organic solvent, and
• drying to form said resist underlayer film.