Surface treatment method for semiconductor substrates and surface treatment agent composition
A surface treatment method for semiconductor substrates 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 bevel region which is formed on a periphery of the pattern formation region, 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 bevel region on the main surface of the semiconductor substrate, in which, with respect to a surface of a silicon oxide substrate brought into contact with the surface treatment agent composition, an IPA receding contact angle is 3° or more at a room temperature of 25° C., and/or a water receding contact angle is 40° 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 bevel region formed on a periphery of the pattern formation region and including an inclined surface formed on the main surface, the method comprising:
a surface treatment step comprising bringing a surface treatment agent composition including a silylating agent and a solvent into contact with the pattern formation region and the bevel region on the main surface of the semiconductor substrate by a spin method, and
after the surface treatment step, a step comprising bringing the main surface of the semiconductor substrate into contact with a rinsing solution, and shaking off the rinsing solution using a spin method,
wherein the surface treatment agent composition exhibits an IPA receding contact angle obtained by the following procedure of 3° or more at a room temperature of 25° C., and/or
a water receding contact angle obtained by the following procedure of 40° or more at the room temperature of 25° C.,
and wherein;
the surface treatment agent composition is brought into contact with a smooth surface of a silicon oxide substrate of which surface is composed of silicon oxide to perform a surface treatment, and
with respect to the surface-treated surface of the silicon oxide substrate in a state of being stood on a horizontal table, 3 μl of 2-propanol is dropped on the surface at the room temperature of 25° C. and a value of a contact angle 60 seconds later after the dropping is measured and defined as the IPA receding contact angle (°), and
30 μl of pure water is dropped on the surface at the room temperature of 25° C., the pure water is sucked at a rate of 6 μl/sec, and a value of a contact angle while a droplet size is decreasing is measured and defined as the water receding contact angle (°).
2 . The treatment method according to claim 1 ,
wherein the solvent includes an aprotic solvent.
3 . The treatment method according to claim 2 ,
wherein the solvent includes the aprotic solvent in a content of 100% by mass in 100% by mass of the solvent.
4 . The treatment method according to claim 2 ,
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.
5 . The treatment method according to claim 2 ,
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) a derivative of polyhydric alcohol.
6 . 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).
7 . 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.
8 . 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.
9 . The treatment method according to claim 1 ,
wherein the surface treatment agent composition includes a catalyst.
10 . The treatment method according to claim 9 ,
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& 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) s 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].
11 . The treatment method according to claim 9 ,
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.
12 . 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.
13 . The treatment method according to claim 1 ,
wherein the IPA receding contact angle is 5° or more at the room temperature of 25° C., and/or
the water receding contact angle is 50° or more at the room temperature of 25° C.
14 . The treatment method according to claim 1 ,
wherein an IPA contact angle measured by the following procedure is 2° or more and 10° or less at the room temperature of 25° C., and/or
a water contact angle measured by the following procedure is 50° or more at the room temperature of 25° C.,
and wherein;
the surface treatment agent composition is brought into contact with a smooth surface of a silicon oxide substrate of which surface is composed of silicon oxide to perform a surface treatment, and
with respect to the surface-treated surface of the silicon oxide substrate in a state of being stood on a horizontal table, 1 μl of 2-propanol is dropped on the surface at the room temperature of 25° C. in a state of a droplet and a value of a contact angle 5 seconds later after the dropping is measured and defined as the IPA contact angle (°), and
1 μl of pure water is dropped on the surface at the room temperature of 25° C. and a value of a contact angle 5 seconds later after the dropping is measured and defined as the water contact angle (°).
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.