JP2024503164A - solvent composition - Google Patents

Abstract

The present invention provides a solvent composition that has EBR performance and pre-wet performance and can suppress the formation of a hump that is formed at the wafer periphery during EBR treatment in a semiconductor manufacturing process. SOLUTION: A solvent composition containing (a) a ketone compound having 5 or more carbon atoms and (b) a lactone compound, wherein the content of (b) is 5 to 90% by mass. [Selection diagram] None

Description

The present invention relates to edge coating removal (EBR) of a wafer, which is performed after coating a coating liquid such as an anti-reflective agent or resist onto a wafer using a spin coater in the process of forming a coating film on a wafer in a semiconductor manufacturing process. It has EBR performance that can suppress the height of the bulge (hump) that occurs at the periphery of the coating film during bead removal, and has the effect of reducing the amount of coating liquid used such as antireflection agent and resist. The present invention relates to a solvent composition having pre-wet performance.

In a lithography process for forming a pattern on a semiconductor wafer, a spin coater is used to apply a coating liquid such as an antireflection agent or a resist onto the wafer surface. At this time, a bead of thickened coating film is formed at the periphery of the wafer, so an EBR process is performed to dissolve and remove this bead using a solvent. In this EBR process, a method is generally used in which a solvent (referred to as EBR solvent) for dissolving and removing the coating film is discharged from a nozzle toward the surface of the coating film in the peripheral area and the back surface of the wafer while rotating the wafer. There is.

After the bead at the periphery of the wafer is dissolved and removed by EBR processing, the wafer has a ring-shaped area where the coating film has been removed and an area where the coating film remains. A raised portion of the coating film called a hump is formed during the EBR treatment at the peripheral edge of the coating film near the boundary between these regions. The ratio of the thickness of the portion of the coating film where the hump is formed divided by the thickness of the flat coating film with no hump formation inside the periphery is called the hump ratio. Since this hump causes a decrease in yield in the lithography process, it is required to suppress the hump in the coating film during EBR processing, that is, to reduce the hump ratio as close to 1 as possible.

Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2017-92445) discloses that when performing EBR processing, gas is sprayed in the circumferential direction from a slit-shaped nozzle near the nozzle from which the removal liquid is ejected, thereby removing the material in contact with the wafer surface. The height of the hump is suppressed by applying force to the liquid in a circumferentially outward direction.

Patent Document 2 (Japanese Unexamined Patent Publication No. 2018-181963) discloses that OK-73 thinner (propylene glycol monomethyl ether (PGME)/propylene glycol monomethyl ether acetate (PGMEA) = 0.7/0.3 mixed liquid) has a high surface tension. By adding dilution water and cooling the solvent and piping, attempts are being made to control the surface tension of the EBR treatment solution and reduce the height of the hump.

Patent Document 3 (Japanese Unexamined Patent Publication No. 2018-121045) attempts to suppress humps by optimizing processing conditions such as the rotation speed of the wafer of a spin coater, the angle of the EBR solvent nozzle, and the EBR processing time during EBR processing. ing.

As described above, attempts have been made to provide a spin coater with a function for suppressing hump and to optimize operating conditions. Other attempts have been made to suppress hump by using an EBR solvent with an appropriate composition for the coating film.

For example, Patent Document 4 (Japanese Unexamined Patent Publication No. 2007-179043) describes a mixture of γ-butyrolactone, anisole, and methyl ethyl ketone (MEK) as a composition of a cleaning liquid for photolithography.

Patent Document 5 (Japanese Unexamined Patent Publication No. 2006-189518) describes a mixture of butyl acetate and cyclohexanone as a composition of a cleaning liquid for lithography.

Patent Document 6 (Japanese Unexamined Patent Publication No. 2007-178589) describes a mixture of butyl acetate and cyclohexanone, and a mixture of butyl acetate, cyclohexanone, and propylene glycol monomethyl ether acetate (PGMEA) as a composition of a cleaning solution for photolithography.

Patent Document 7 (Japanese Unexamined Patent Publication No. 11-218933) describes a mixture of propylene glycol monomethyl ether (PGME), methyl ethyl ketone (MEK), and γ-butyrolactone as a composition of a solvent for cleaning and removing resist.

JP2017-92445A JP 2018-181963 Publication Japanese Patent Application Publication No. 2018-121045 Japanese Patent Application Publication No. 2007-179043 Japanese Patent Application Publication No. 2006-189518 Japanese Patent Application Publication No. 2007-178589 Japanese Patent Application Publication No. 11-218933

On the other hand, coating solutions such as anti-reflective agents and resists are particularly expensive, so in order to reduce the amount of these coating solutions used and apply them uniformly, the wafer should be coated immediately before spin coating. The entire surface is coated with a suitable solvent. This is called pre-wet processing.

When different solvents are used for pre-wet treatment and EBR treatment, piping lines, tanks, etc. must be installed for each solvent. A solvent composition known as OK-73 thinner (PGME/PGMEA = 0.7/0.3) is conventionally used for EBR processing and pre-wet processing. However, OK-73 thinner has a problem in that it has a high hump ratio after EBR treatment. Therefore, it is desirable to develop a solvent composition that can suppress hump formation and has performance in both EBR processing and prewet processing.

SUMMARY OF THE INVENTION An object of the present invention is to provide a solvent composition that has EBR performance and pre-wet performance and can suppress the formation of a hump that is formed at the wafer peripheral edge during EBR treatment in a semiconductor manufacturing process.

The present invention has been made in view of the above circumstances, and the present inventors have intensively studied the composition of the solvent composition. As a result, the present inventors found that a solvent composition containing a specific ketone compound and a lactone compound can suppress the formation of a hump formed at the wafer peripheral edge during EBR processing, and has prewet performance. I discovered that.
That is, the present invention includes the following [1] to [20].
[1]
A solvent composition containing (a) a ketone compound having 5 or more carbon atoms and (b) a lactone compound, wherein the content of (b) is 5 to 90% by mass.
[2]
The solvent composition according to [1], wherein the (a) is a cyclic ketone compound.
[3]
The solvent composition according to [2], wherein (a) is cyclohexanone.
[4]
The solvent composition according to any one of [1] to [3], wherein (b) is γ-butyrolactone.
[5]
The solvent composition according to any one of [1] to [4], wherein the content of (a) is 5 to 80% by mass.
[6]
Furthermore, (c) the solvent according to any one of [1] to [5], which contains at least one member selected from the group consisting of alkylene glycol alkyl ethers and carboxylic acid esters thereof, represented by the following formula (1). Composition.
R ¹ O(C _n H _2n O) _x R ² (1)
(In formula (1), R ¹ is an alkyl group selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. represents a group. R ² represents a hydrogen atom or an acyl group selected from the group consisting of -COCH ₃ , -COC ₂ H ₅ , -COC ₃ H ₇ and -COC ₄ H _9. n is 2 or 3; (x is an integer from 1 to 4.)
[7]
The solvent composition according to [6], wherein the content of (c) is 5 to 80% by mass.
[8]
The content of (a) is 5 to 70% by mass, the content of (b) is 5 to 60% by mass, and the content of (c) is 5 to 70% by mass, according to [6]. Solvent composition.
[9]
The solvent composition according to any one of [6] to [8], wherein (c) is propylene glycol monomethyl ether.
[10]
The solvent composition according to any one of [6] to [8], wherein the (c) is propylene glycol monomethyl ether acetate.
[11]
The solvent composition according to any one of [6] to [8], wherein the (c) contains both propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
[12]
The solvent composition according to any one of [1] to [11], which is formed by applying a coating liquid to a substrate and is used to remove an unnecessary coating film attached to an edge of the substrate.
[13]
The solvent composition according to [12], wherein the coating liquid is at least one selected from the group consisting of a resist and an antireflection agent.
[14]
The solvent composition according to any one of [1] to [13], which is used for pre-wetting a substrate.
[15]
[1] Using the solvent composition according to any one of [11], applying a coating liquid to a substrate to form the unnecessary coating film attached to the edge of the substrate, including removing the unnecessary coating film, EBR processing method.
[16]
The EBR processing method according to [15], wherein the coating liquid is at least one selected from the group consisting of a resist and an antireflection agent.
[17]
A method for prewetting a substrate, the method comprising prewetting the substrate using the solvent composition according to any one of [1] to [11].
[18]
Use of the solvent composition according to any one of [1] to [11] for removing an unnecessary coating film formed by applying a coating liquid to a substrate and attached to an edge of the substrate.
[19]
The use according to [18], wherein the coating liquid is at least one selected from the group consisting of a resist and an antireflection agent.
[20]
Use of the solvent composition according to any one of [1] to [11] for prewetting a substrate.

The solvent composition of the present invention has EBR performance and pre-wet performance, and can suppress the formation of a hump that is formed at the wafer periphery during EBR treatment in a semiconductor manufacturing process.

Preferred embodiments of the present invention will be described below, but it should be understood that the present invention is not limited to these embodiments, and that various applications are possible within the spirit and scope of implementation.

[Solvent composition]
The solvent composition contains (a) a ketone compound having 5 or more carbon atoms and (b) a lactone compound, and the content of (b) in the solvent composition is 5 to 90% by mass.

(a) Ketone compound having 5 or more carbon atoms The ketone compound can be used without particular limitation as long as it is a ketone compound having 5 or more carbon atoms. From the viewpoint of availability, the ketone compound preferably has 5 to 11 carbon atoms, more preferably 5 to 7 carbon atoms. By having 5 or more carbon atoms, the flash point does not become too low, and requirements for equipment, work environment, etc. in the production and use of the solvent composition can be reduced.

The ketone compound may be cyclic or acyclic. Examples of the cyclic ketone compound include 2-methylcyclobutanone, cyclopentanone, 2-methylcyclopentanone, 2,5-dimethylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, and cycloheptanone. Examples of acyclic ketone compounds include 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-2-hexanone, -heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-undecanone and the like. The ketone compound is preferably a cyclic ketone compound, and among the above-mentioned cyclic ketone compounds, cyclohexanone is more preferable.

The content of (a) in the solvent composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass.

(b) Lactone compound The lactone compound can be used without particular restriction. The lactone compound preferably has 4 to 9 carbon atoms, more preferably 4 to 6 carbon atoms. The lactone compound preferably has 4 to 7 ring members, more preferably 5 or 6 ring members. Preferred lactone compounds include γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, β-valerolactone, ε-caprolactone, γ-nonalactone, and the like. Among the lactone compounds mentioned above, γ-butyrolactone is preferred from the viewpoint of easy availability.

The content of (b) in the solvent composition is 5 to 90% by mass, preferably 10 to 70% by mass, more preferably 15 to 50% by mass, and 20 to 45% by mass. It is even more preferable that there be.

(c) Alkylene glycol alkyl ether The solvent composition may further contain (c) at least one selected from the group consisting of alkylene glycol alkyl ether and its carboxylic acid ester, represented by the following formula (1). preferable.
R ¹ O(C _n H _2n O) _x R ² (1)
(In formula (1), R ¹ is an alkyl group selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. represents a group. R ² represents a hydrogen atom or an acyl group selected from the group consisting of -COCH ₃ , -COC ₂ H ₅ , -COC ₃ H ₇ and -COC ₄ H _9. n is 2 or 3; (x is an integer from 1 to 4.)
When R ² is a hydrogen atom, formula (1) represents an alkylene glycol alkyl ether, and when R ² is an acyl group, formula (1) represents a carboxylic acid ester of an alkylene glycol alkyl ether. R ² is preferably a hydrogen atom or -COCH ₃ (acetyl group).

Examples of the alkylene glycol alkyl ether represented by formula (1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl. Examples include ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and the like. Examples of the carboxylic acid ester of alkylene glycol alkyl ether represented by formula (1) include acetate, propionate, butyrate, and the like of the above-mentioned alkylene glycol alkyl ether.

The content of (c) in the solvent composition is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, and even more preferably 15 to 70% by mass.

The content of (c) relative to the total of (a), (b) and (c) is preferably 5 to 70% by mass, more preferably 7 to 65% by mass, and 10 to 55% by mass. It is more preferable that

In one embodiment, (c) is preferably propylene glycol monomethyl ether. When (c) is propylene glycol monomethyl ether, the content of propylene glycol monomethyl ether in the solvent composition is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and 15% by mass. More preferably, the amount is 50% by mass.

In another embodiment, (c) is preferably propylene glycol monomethyl ether acetate. When (c) is propylene glycol monomethyl ether acetate, the content of propylene glycol monomethyl ether acetate in the solvent composition is preferably 5 to 50% by mass, more preferably 10 to 45% by mass. , more preferably 15 to 40% by mass.

In yet another embodiment, (c) preferably includes both propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA). In this case, the mass ratio of propylene glycol monomethyl ether (PGME) to propylene glycol monomethyl ether acetate (PGMEA) is preferably PGME/PGMEA = 1.0 to 3.0, and preferably 1.5 to 2.5. It is more preferable. The total content of propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA) in the solvent composition is preferably 5 to 50% by mass, more preferably 7 to 45% by mass. , more preferably 10 to 40% by mass.

When the solvent composition contains (c), the content of (a) is 5 to 70% by mass, the content of (b) is 5 to 80% by mass, and the content of (c) is 5 to 70% by mass. The content of (a) is preferably 10 to 60% by mass, the content of (b) is 10 to 60% by mass, and the content of (c) is more preferably 10 to 50% by mass.

When (c) is propylene glycol monomethyl ether, the content of (a) is 10 to 70% by mass, the content of (b) is 5 to 60% by mass, and the content of propylene glycol monomethyl ether is 10 to 70% by mass. %, the content of (a) is 15 to 60% by mass, the content of (b) is 10 to 50% by mass, and the content of propylene glycol monomethyl ether is 15 to 50% by mass. More preferred.

When (c) is propylene glycol monomethyl ether acetate, the content of (a) is 5 to 60% by mass, the content of (b) is 10 to 70% by mass, and the content of propylene glycol monomethyl ether acetate is 5 to 60% by mass. It is preferable that the content of (a) is 10 to 50% by mass, the content of (b) is 20 to 55% by mass, and the content of propylene glycol monomethyl ether acetate is 10 to 45% by mass. It is more preferable that there be.

When (c) contains both propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, the content of (a) is 5 to 60% by mass, the content of (b) is 10 to 80% by mass, and propylene glycol monomethyl ether It is preferable that the total content of propylene glycol monomethyl ether acetate is 5 to 50% by mass, the content of (a) is 10 to 50% by mass, the content of (b) is 20 to 75% by mass, and propylene glycol More preferably, the total content of monomethyl ether and propylene glycol monomethyl ether acetate is 7 to 45% by mass.

[Coating film]
The solvent composition can be applied to various coating films such as antireflection films and resist films. The coating film is formed by applying a coating liquid onto a substrate such as a silicon wafer using a spin coater or the like. The coating liquid is preferably at least one selected from the group consisting of a resist and an antireflection agent.

The resist may be either positive or negative; examples include rubber-based negative resist, G-line photoresist, i-line photoresist, KrF photoresist, ArF photoresist, EUV photoresist, and electron beam photoresist. Examples include photoresist. Chemically amplified resists containing photoacid generators can also be used. A resist that can be developed with an alkaline aqueous solution is preferably used. Specifically, for example, a positive resist containing a naphthoquinone diazide compound and a base resin such as a novolak resin, a photoacid generator, a compound that increases its solubility in an aqueous alkali solution when decomposed by an acid, and an alkali-soluble resin. A positive resist containing a photoacid generator, a positive resist containing an alkali-soluble resin having a group that decomposes with an acid and increases solubility in an aqueous alkaline solution, a photoacid generator, a crosslinking agent, and a photoacid generator. , and an alkali-soluble resin. Examples of the base resin of the resist include novolac resin, polyhydroxystyrene, (meth)acrylic resin, polymer of (meth)acrylic acid ester, hydroxystyrene (meth)acrylic acid copolymer, and silsesquioxane. “(Meth)acrylic” is a general term for acrylic and methacrylic.

As the antireflective agent, a known antireflective agent can be used, and examples include organic antireflective agents, silicon-containing antireflective (SiARC) agents, and the like.

Examples of organic antireflection agents include compositions containing a light-absorbing compound and a resin, compositions containing a resin having light-absorbing groups connected by chemical bonds and a crosslinking agent, and compositions containing a light-absorbing compound and a crosslinking agent. and a composition containing a light-absorbing polymer crosslinking agent.

Examples of light-absorbing compounds include benzophenone, benzotriazole, azo compounds, naphthalene, anthracene, anthraquinone, triazine, and derivatives thereof.

Examples of resins include polyester, polyimide, polystyrene, poly(4-hydroxystyrene), copolymers of 4-hydroxystyrene and alkyl methacrylates, alkyl acrylates and/or styrene, novolac resins, polyacetal resins, (meth)acrylic resins, Examples include alicyclic polymers such as polyvinyl alcohol, fluorocarbon polymers, polymers having a naphthalene skeleton, polymers having a norbornene skeleton, and maleic anhydride copolymers.

Examples of the resin having a light-absorbing group connected by a chemical bond include resins having a light-absorbing aromatic ring structure such as an anthracene ring, a naphthalene ring, a benzene ring, a quinoline ring, a quinoxaline ring, and a thiazole ring. In particular, (meth)acrylic resins and novolak resins having anthracene ring, naphthalene ring, and benzene ring structures are preferably used.

Examples of the crosslinking agent include melamine, benzoguanamine, urea, and glycoluril in which the hydrogen atom of an amino group is substituted with at least one selected from the group consisting of a methylol group and an alkoxymethyl group.

The silicon-containing antireflective agent is a composition containing a silicon-containing polymer, and uses a silicon-silicon σ bond as a light absorption site for ArF light (193 nm). Silicon-containing polymers include polysilanes with pendant phenyl groups; polyolefins with pendant silicon-containing groups, poly(meth)acrylates, polyvinyl alcohols, polyvinylphenols, polyvinylmaleimides, cellulose, amylose, dextran, pullulan, and derivatives thereof. Can be mentioned.

[EBR processing method]
The solvent composition is suitably used for EBR processing. The EBR process is a process for removing unnecessary coating films attached to the edges of a substrate coated with a coating liquid. The EBR treatment method using the solvent composition is not particularly limited, and can be carried out by any method known in the art. For example, while a substrate with a coating film formed on its surface is held in a rotating holding unit and rotated, a solvent composition is discharged from a nozzle toward a position a predetermined distance inside the outer edge of the coating film, and as needed. Perform drying treatment accordingly.

The hump ratio after EBR treatment is preferably 1.5 or less, more preferably 1.4 or less, and even more preferably 1.3 or less.

[Pre-wet processing method]
The solvent composition is suitably used for pre-wet treatment. The prewet treatment method using the solvent composition is not particularly limited, and can be carried out by any method known in the art. For example, the substrate is held by a rotating holding part, and while the solvent composition is discharged from a nozzle, the rotation of the substrate is started and the solvent is applied to the entire surface of the substrate by centrifugal force. By applying the coating liquid after the pre-wet treatment, the amount of the coating liquid used can be reduced.

[substrate]
The substrate to which the solvent composition is applied is not particularly limited. Examples include silicon wafers, glass substrates, metal substrates, and the like.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples in any way.

In the following Examples and Comparative Examples, the following antireflective agents or resists were used.
Antireflective agent A: “ODL301” manufactured by Shin-Etsu Chemical Co., Ltd.
Antireflective agent B: “LT8003” manufactured by Nissan Chemical Co., Ltd.
Anti-reflective agent C: "HM918" manufactured by Nissan Chemical Co., Ltd. (silicon-based anti-reflective agent)
Anti-reflective agent D: “SHB961” manufactured by Shin-Etsu Chemical Co., Ltd. (silicon-based anti-reflective agent)
Resist A: “X198” manufactured by Shin-Etsu Chemical Co., Ltd. (chemically amplified resist)
Resist B: "P6255" manufactured by Tokyo Ohka Kogyo Co., Ltd. (chemically amplified resist, base resin: acrylic resin)

1. Preparation of solvent composition [Example 1]
6.0 g of cyclohexanone (electronic industry grade product manufactured by Showa Denko K.K.) and 54.0 g of γ-butyrolactone (electronic industry grade product manufactured by Showa Denko K.K.) were placed in a 110 mL glass sample bottle at room temperature in the air. The solvent composition of Example 1 was prepared by weighing and mixing.
[Examples 2 to 22, Comparative Examples 1 to 7]
In the same manner as in Example 1, solvent compositions having the compositions shown in Table 1 were prepared. Propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA) in the composition shown in Table 1 were electronic industry grade products manufactured by Showa Denko K.K.

2. EBR treatment test Coating films of antireflection agents A to D or resists A to B were formed according to the following procedure, and the hump ratio after EBR treatment was calculated.

[EBR treatment test of antireflection agent A]
(1) Pre-wet treatment A 6-inch silicon wafer was set on the wafer holder (spin chuck) of a spin coater (ACT-300AIIS, manufactured by Active Co., Ltd.), and PGME:PGMEA=0. 1.5 to 2.0 g of a treatment liquid (composition known as OK-73 thinner) consisting of 700:0.300 (mass ratio) was dispensed from the nozzle. Thereafter, the wafer was rotated at a rotational speed of 1000 rpm for 10.5 seconds to perform a pre-wet process in which the wafer surface was coated with a solvent.
(2) Application of anti-reflective agent Spin coat 0.2 to 0.25 g of anti-reflective agent A on the pre-wet wafer at a rotation speed of 1300 rpm for 30 seconds and at a rotation speed of 700 rpm for 3 seconds to coat the entire wafer. An antireflection film with a thickness of 100 nm was formed.
(3) EBR treatment The wafer on which the anti-reflection film was formed was rotated at 1000 rpm, and 8 g of the solvent composition shown in Table 1 was released over 20 seconds toward a position 2 mm from the edge of the wafer to remove the coating film. The peripheral portion was cleaned and removed. Furthermore, the cleaning area was air-dried by holding the rotation speed at 3000 rpm for 20 seconds.
(4) Baking treatment The wafer after EBR treatment is placed on a hot plate heated to 250°C for 60 seconds to perform baking treatment, and then placed on a hot plate heated to 350°C for 60 seconds to perform baking treatment, and then placed at room temperature. cooled down to.
(5) Calculation of hump ratio Scan the thickness of the peripheral and flat parts of the anti-reflection film formed on the silicon wafer using a contact profiler (manufactured by KLA-TENCOR, P-12). It was measured with The height of the hump (height from the surface of the silicon wafer to the top of the hump) is calculated from the thickness of the anti-reflective film (from the surface of the silicon wafer to the flat part located from the periphery of the anti-reflective film toward the center of the wafer). The hump ratio was calculated by dividing by the height of The results are shown in Table 1.

[EBR treatment test of antireflection agent B]
The hump ratio after EBR treatment was calculated in the same manner as in "EBR treatment test of antireflection agent A" except that operations (2) and (4) were performed as follows.
(2) Application of anti-reflective agent Apply 0.2 to 0.25 g of anti-reflective agent B on the pre-wet wafer at a rotation speed of 2000 rpm for 30 seconds, at a rotation speed of 3000 rpm for 5 seconds, and at a rotation speed of 2000 rpm for 5 seconds. An antireflection film with a thickness of 190 nm was formed on the entire wafer by spin coating.
(4) Baking treatment The wafer after EBR treatment was placed on a hot plate heated to 180°C for 60 seconds to perform baking treatment, and then placed on a hot plate heated to 350°C for 60 seconds to perform baking treatment, and then placed at room temperature. cooled to.

[EBR treatment test of antireflection agent C]
The hump ratio after EBR treatment was calculated in the same manner as in "EBR treatment test of antireflection agent A" except that operations (2) and (4) were performed as follows.
(2) Application of anti-reflective agent Spin-coat 0.2 to 0.25 g of anti-reflective agent C on the pre-wet wafer at a rotation speed of 2700 rpm for 30 seconds and at a rotation speed of 700 rpm for 3 seconds to coat the entire wafer. An antireflection film with a thickness of 40 nm was formed.
(4) Baking treatment The wafer after EBR treatment was placed on a hot plate at 220° C. for 60 seconds to perform baking treatment, and then cooled to room temperature.

[EBR treatment test of antireflection agent D]
The hump ratio after EBR treatment was calculated in the same manner as in "EBR treatment test of antireflection agent A" except that operations (2) and (4) were performed as follows.
(2) Application of anti-reflective agent Spin-coat 0.2 to 0.25 g of anti-reflective agent D on the pre-wet wafer at a rotation speed of 1250 rpm for 30 seconds and at a rotation speed of 700 rpm for 3 seconds to coat the entire wafer. An antireflection film with a thickness of 40 nm was formed.
(4) Baking treatment The wafer after EBR treatment was placed on a hot plate at 220° C. for 60 seconds to perform baking treatment, and then cooled to room temperature.

[EBR processing test of resist A]
The hump ratio after EBR treatment was calculated in the same manner as in "EBR treatment test of antireflection agent A" except that operations (2) and (4) were performed as follows.
(2) Application of resist Spin coat 0.2 to 0.25 g of resist A on the pre-wet-treated wafer at a rotation speed of 1000 rpm for 30 seconds, at a rotation speed of 3000 rpm for 5 seconds, and for 5 seconds at a rotation speed of 2000 rpm. A resist film with a thickness of 100 nm was formed over the entire wafer.
(4) Baking treatment The wafer after EBR treatment was placed on a hot plate at 100° C. for 60 seconds to perform baking treatment, and then cooled to room temperature.

[EBR processing test of resist B]
The hump ratio after EBR treatment was calculated in the same manner as in "EBR treatment test of antireflection agent A" except that operations (2) and (4) were performed as follows.
(2) Application of resist Spin coat 0.2 to 0.25 g of resist B on the prewet-treated wafer at a rotation speed of 1000 rpm for 40 seconds, at a rotation speed of 3000 rpm for 5 seconds, and at a rotation speed of 2000 rpm for 5 seconds. A resist film with a thickness of 90 nm was formed over the entire wafer.
(4) Baking treatment The wafer after EBR treatment was placed on a hot plate at 120° C. for 60 seconds to perform baking treatment, and then cooled to room temperature.

3. Pre-wet treatment test The performance of the solvent compositions shown in Table 1 as pre-wet treatment liquids was evaluated according to the following procedure.
(1) Pre-wet treatment A 6-inch silicon wafer was set on the wafer holder (spin chuck) of a spin coater (ACT-300AIIS, manufactured by Active Co., Ltd.), and solvent composition 1 of Table 1 was placed in the center of the stationary wafer. .5 g was dispensed through the nozzle. Thereafter, the wafer was rotated at a rotation speed of 1000 rpm for 10.5 seconds to perform a pre-wet treatment in which the wafer surface was coated with a solvent composition.
(2) Application of anti-reflective agent Spin-coat anti-reflective agent D on the pre-wet-treated wafer at a rotation speed of 1250 rpm for 30 seconds and at a rotation speed of 700 rpm for 3 seconds to form an anti-reflection film with a thickness of 40 nm over the entire wafer. was formed.
(3) Performance evaluation Based on the case where the solvent composition of Comparative Example 5 was used as the pre-wet treatment liquid, the amount of antireflection agent D required to coat the entire wafer was compared, and the antireflection agent D was determined as follows. The effect of reducing the amount of agent used was evaluated. The composition of Comparative Example 5 (PGME:PGMEA=0.700:0.300 (mass ratio)) is known as OK-73 thinner, and is a composition commonly used as a pre-wet treatment liquid.
Pass: The amount of antireflection agent used was smaller than in Comparative Example 5.
Rejected: The amount of antireflection agent used was larger than in Comparative Example 5.

Claims (17)

A solvent composition containing (a) a ketone compound having 5 or more carbon atoms and (b) a lactone compound, wherein the content of (b) is 5 to 90% by mass. The solvent composition according to claim 1, wherein the (a) is a cyclic ketone compound. 3. The solvent composition according to claim 2, wherein said (a) is cyclohexanone. The solvent composition according to any one of claims 1 to 3, wherein the (b) is γ-butyrolactone. The solvent composition according to any one of claims 1 to 4, wherein the content of (a) is 5 to 80% by mass. The solvent according to any one of claims 1 to 5, further comprising (c) at least one selected from the group consisting of alkylene glycol alkyl ethers and carboxylic acid esters thereof, represented by the following formula (1). Composition.
R ¹ O(C _n H _2n O) _x R ² (1)
(In formula (1), R ¹ is an alkyl group selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. represents a group. R ² represents a hydrogen atom or an acyl group selected from the group consisting of -COCH ₃ , -COC ₂ H ₅ , -COC ₃ H ₇ and -COC ₄ H _9. n is 2 or 3; (x is an integer from 1 to 4.) The solvent composition according to claim 6, wherein the content of (c) is 5 to 80% by mass. 7. The content of (a) is 5 to 70% by mass, the content of (b) is 5 to 60% by mass, and the content of (c) is 5 to 70% by mass. Solvent composition. The solvent composition according to any one of claims 6 to 8, wherein said (c) is propylene glycol monomethyl ether. The solvent composition according to any one of claims 6 to 8, wherein (c) is propylene glycol monomethyl ether acetate. A solvent composition according to any one of claims 6 to 8, wherein (c) comprises both propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. The solvent composition according to any one of claims 1 to 11, which is formed by applying a coating liquid to a substrate and is used to remove an unnecessary coating film attached to an edge of the substrate. The solvent composition according to claim 12, wherein the coating liquid is at least one selected from the group consisting of a resist and an antireflection agent. The solvent composition according to any one of claims 1 to 13, used for pre-wetting a substrate. The method comprises removing an unnecessary coating film formed by applying a coating liquid to a substrate using the solvent composition according to any one of claims 1 to 11 and adhering to an end portion of the substrate. EBR processing method. The EBR processing method according to claim 15, wherein the coating liquid is at least one selected from the group consisting of a resist and an antireflection agent. A method of prewetting a substrate, comprising prewetting the substrate with a solvent composition according to any one of claims 1 to 11.