Surface treatment method for semiconductor substrates and surface treatment agent composition

Patent metadata

Field	Value
Publication number	US-2023282474-A1
Application number	US-202117999363-A
Country	US
Kind code	A1
Filing date	May 19, 2021
Priority date	May 21, 2020
Publication date	Sep 7, 2023
Grant date	—

Abstract

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.

First claim

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 which is formed on a periphery of the pattern formation region, the method comprising:
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, wherein an IPA receding contact angle obtained by the following procedure is 3° or more at a room temperature of 25° C., and/or a water receding contact angle obtained by the following procedure is 400 or more at the room temperature of 25° C., (procedure) 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 - 3 . (canceled)

4 . The treatment method according to claim 1 ,
wherein the surface treatment agent composition includes a solvent.

5 . The treatment method according to claim 4 ,
wherein the solvent includes an aprotic solvent.

6 . The treatment method according to claim 5 ,
wherein the solvent includes the aprotic solvent in a content of 100% by mass in 100% by mass of the solvent.

7 . The treatment method according to claim 5 ,
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.

8 . The treatment method according to claim 5 ,
wherein the solvent includes at least one of following (i), (ii) and (iii), (i) carbonate solvent or a lactone (ii) propylene carbonate or γ-butyrolactone, and (iii) a derivative of polyhydric alcohol.

9 - 10 . (canceled)

11 . 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).

12 . 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.

13 . (canceled)

14 . 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.

15 . The treatment method according to claim 1 ,
wherein the surface treatment agent composition includes a catalyst.

16 . The treatment method according to claim 15 ,
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) 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 t is 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

Assignees

• Central Glass Co Ltd

Inventors

• Okumura Yuzo
• Fukui Yuki
• Shiota Saori
• Terui Yoshiharu
• Kumon Soichi

Classifications

• H10P70/23 Primary

  during, before or after processing of insulating materials · CPC title

• H10P95/00

  Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass · CPC title

• H10P70/20 Primary

  Cleaning during device manufacture · CPC title

• H10P70/00

  Cleaning of wafers, substrates or parts of devices · CPC title

• C11D2111/22

  Electronic devices, e.g. PCBs or semiconductors · CPC title