Surface treatment method for semiconductor substrate and surface treatment agent composition
A surface treatment method for a semiconductor substrate of the present invention is a treatment method of treating a main surface of a semiconductor substrate that has, on the main surface of the substrate, a pattern formation region in which a pattern having a concave-convex structure with a pattern dimension of 30 nm or less is formed and a pattern non-formation region in which no pattern is formed, the method including a surface treatment step of bringing a surface treatment agent composition including a silylating agent into contact with the pattern formation region and the pattern non-formation region on the main surface of the semiconductor substrate, in which, with respect to a surface of the pattern non-formation region after the surface treatment step, an IPA contact angle with 2-propanol is 2° or more at a room temperature of 25° C. and/or a water contact angle with pure water is 50° or more at the room temperature of 25° C.
1 . A treatment method of treating a main surface of a semiconductor substrate that has, on the main surface of the substrate, a pattern formation region in which a pattern having a concave-convex structure with a pattern dimension of 30 nm or less is formed and a pattern non-formation region in which no pattern is formed, the method comprising:
a surface treatment step of bringing a surface treatment agent composition including a silylating agent and a solvent into contact with the pattern formation region and the pattern non-formation region on the main surface of the semiconductor substrate, and
an evaluation step of determining whether or not, with respect to a surface of the pattern non-formation region after the surface treatment step, an IPA contact angle with 2-propanol is 2° or more at a room temperature of 25° C. and/or a water contact angle with pure water is 50° or more at the room temperature of 25° C., which is obtained by dropping 1 μl of droplets of 2-propanol or pure water on the substrate surface of the pattern non-formation region at the room temperature of 25° C. in a state in which the semiconductor substrate is stood on a horizontal table, and then measuring after 5 seconds.
2 . The treatment method according to claim 1 ,
wherein the surface treatment step is a step of forming a surface treatment agent layer on an entire main surface of the semiconductor substrate, and
on a surface of the surface treatment agent layer, the IPA contact angle is 2° or more at the room temperature of 25° C. and/or the water contact angle is 55° or more at the room temperature of 25° C.
3 . The treatment method according to claim 1 ,
wherein the solvent includes an aprotic solvent.
4 . The treatment method according to claim 3 ,
wherein the solvent includes the aprotic solvent in a content of 100% by mass in 100% by mass of the solvent.
5 . The treatment method according to claim 3 ,
wherein the aprotic solvent includes one or two or more kinds selected from the group consisting of hydrocarbons, esters, ethers, ketones, halogen element-containing solvents, sulfoxides, carbonate solvents, derivatives of polyhydric alcohol, nitrogen element-containing solvents, and silicone solvents.
6 . The treatment method according to claim 3 ,
wherein the solvent includes at least one of following (i), (ii) and (iii),
(i) a carbonate solvent or a lactone,
(ii) propylene carbonate or γ-butyrolactone, and
(iii) one or two or more kinds selected from the group consisting of derivatives of polyhydric alcohol, hydrocarbons, and ethers.
7 . The treatment method according to claim 1 ,
wherein the silylating agent includes a silicon compound represented by General Formula [1],
R 1 a Si(H) b X 4-a-b [1]
(in General Formula [1], R 1 's each independently represent an organic group including a hydrocarbon group having 1 to 18 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, X's each independently represent a monovalent functional group in which an element bonded to an Si element is nitrogen, oxygen, carbon, or halogen, a represents an integer of 1 to 3, b represents an integer of 0 to 2, and a sum of a and b is 1 to 3).
8 . The treatment method according to claim 1 ,
wherein the silylating agent has a trialkylsilyl group, or an element bonded to an Si element, or both are nitrogen.
9 . The treatment method according to claim 1 ,
wherein a content of the silylating agent is 0.1% by mass or more and 50% by mass or less in 100% by mass of the surface treatment agent composition.
10 . The treatment method according to claim 1 ,
wherein the surface treatment agent composition includes a catalyst.
11 . The treatment method according to claim 10 ,
wherein the catalyst includes one or two or more kinds selected from the group consisting of trimethylsilyltrifluoroacetate, trimethylsilyltrifluoromethanesulfonate, dimethylsilyltrifluoroacetate, dimethylsilyltrifluoromethanesulfonate, butyldimethylsilyltrifluoroacetate, butyldimethylsilyltrifluoromethanesulfonate, hexyldimethylsilyltrifluoroacetate, hexyldimethylsilyltrifluoromethanesulfonate, octyldimethylsilyltrifluoroacetate, octyldimethylsilyltrifluoromethanesulfonate, decyldimethylsilyltrifluoroacetate, decyldimethylsilyltrifluoromethanesulfonate, a sulfonic acid represented by General Formula [3], an anhydride of the sulfonic acid, a salt of the sulfonic acid, a sulfonic acid derivative represented by General Formula [4], a sulfonate represented by General Formula [5], a sulfonimide represented by each of General Formulae [6] and [7], a sulfonimide derivative represented by each of General Formulae [8] and [9], a sulfonmethide represented by General Formula [10], a sulfonmethide derivative represented by General Formula [11], an acid imidized product, a nitrogen-containing compound, a nitrogen-containing heterocyclic compound, and a silylated heterocyclic compound,
R 8 —S(═O) 2 OH [3]
[in General Formula [3], R 8 represents a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, and a hydroxyl group]
R 8′ —S(═O) 2 O—Si(H) 3-r (R 9 ) r [4]
[in General Formula [4], R 8′ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, R 9 's each independently represent at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, and r represents an integer of 1 to 3]
R 10 —S(═O) 2 OR 11 [5]
[in General Formula [5], R 10 represents a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, and a fluorine element, and R 11 represents a monovalent alkyl group having 1 to 18 carbon atoms]
(R 12 —S(═O) 2 ) 2 NH [6]
[in General Formula [6], R 12 's each independently represent a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, and a fluorine element]
[in General Formula [7], R 13 represents a divalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements]
((R 14 —S(═O) 2 ) 2 N) 5 Si(H) t (R 15 ) 4-s-t [8]
[in General Formula [8], R 14 's each independently represent a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, and a fluorine element, R 15 's each independently represent a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, s represents an integer of 1 to 3, t represents an integer of 0 to 2, and a sum of s and tis 3 or less]
[in General Formula [9], R 16 's each independently represent a divalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, R 17 's each independently represent a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, u represents an integer of 1 to 3, v represents an integer of 0 to 2, and a sum of u and v is 3 or less]
(R 18 —S(═O) 2 ) 3 CH [10]
[in General Formula [10], R 18 's each independently represent a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, and a fluorine element]
((R 19 —S(═O) 2 ) 3 C) w Si(H) x (R 20 ) 4-w-x [11]
[in General Formula [11], R 19 's each independently represent a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, and a fluorine element, R 20 's each independently represent a monovalent hydrocarbon group having 1 to 18 carbon atoms, in which a part or all of hydrogen elements may be replaced with fluorine elements, w represents an integer of 1 to 3, x represents an integer of 0 to 2, and a sum of w and x is 3 or less].
12 . The treatment method according to claim 10 ,
wherein a content of the catalyst is 0.005% by mass or more and 20% by mass or less in 100% by mass of the surface treatment agent composition.
13 . The treatment method according to claim 1 ,
wherein the surface treatment agent composition does not contain water or contains water in a content of 2% by mass or less in 100% by mass of the surface treatment agent composition.
14 . The treatment method according to claim 1 , further comprising, after the surface treatment step:
a drying step of drying the main surface of the semiconductor substrate.
15 . The treatment method according to claim 1 , further comprising, after the surface treatment step:
a removal step of removing a surface treatment agent layer formed on the main surface of the semiconductor substrate from the main surface, the surface treatment agent layer being formed by the surface treatment step.