JP2008239701A - Manufacturing method of surface-treated base material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a surface-treated base material. <P>SOLUTION: The manufacturing method of a surface-treated base material comprises applying a fluorine-containing surface-modifying agent comprising a fluorine-containing compound (F) bearing a fluorine-containing cyclic saturated hydrocarbon group (F<SP>U</SP>) and a reactive group (A<SP>U</SP>) to a base material (S) and subsequently causing the agent to react. For example, the fluorine-containing cyclic saturated hydrocarbon group (F<SP>U</SP>) is an n-valent group obtained by removing n pieces of hydrogen atoms of a cyclic saturated hydrocarbon compound selected from the group consisting of compounds (1)-(5) below (wherein n is an integer of 1-4), where at least 50% of the remaining hydrogen atoms are replaced by a fluorine atom. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a surface-treated substrate, preferably a method for producing a surface-treated substrate used in an immersion lithography method.

Fluoro-based surface modifiers are excellent in various physical properties (water / oil repellency, heat resistance, chemical resistance, transparency, etc.), and as antifouling agents, mold release agents, lubricants, water / oil repellants, etc. Useful.
As the fluorine-containing compound used for the fluorine-based surface modifier, for example, a fluorine-containing compound having a reactive silyl group and a fluorine-containing acyclic alkyl group (CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ etc.) is known.

  On the other hand, knowledge about the water / oil repellency of a compound having a highly fluorinated cyclic hydrocarbon group has not been obtained. For example, Patent Document 1 describes the photoresist characteristics (optical characteristics, etching resistance and acid resistance) of polymers of the following compounds, but does not describe the water repellency of the polymers.

  By the way, in the manufacture of an integrated circuit such as a semiconductor, the pattern image of the mask obtained by irradiating the mask with light from an exposure light source is projected onto a photosensitive resist layer on a substrate through a projection lens, and the pattern is obtained. Lithographic methods are used that transfer the image to the photosensitive resist layer. Usually, the pattern image is projected onto a desired position of the photosensitive resist layer through a projection lens that moves relatively on the photosensitive resist.

  In recent years, a lithography method using a phenomenon in which the wavelength of light in a liquid medium is a reciprocal of the refractive index of the liquid medium, that is, a liquid medium having a high refractive index (between the lower part of the projection lens and the upper part of the photosensitive resist). An immersion lithography method including a step of projecting a pattern image of a mask onto a photosensitive resist while being filled with ultrapure water or the like (hereinafter also referred to as an immersion liquid) has been studied.

In the immersion lithography method, the immersion liquid moves following the projection lens that moves at high speed on the photosensitive resist layer. Therefore, when the projection lens moves to the vicinity of the end face of the photosensitive resist layer, there is a concern that the immersion liquid goes around the end face or the back face of the base material and contaminates the base material, and consequently the exposure apparatus.
Therefore, Patent Document 2 describes that the surface of the base material is subjected to a water repellent treatment with a fluorine-based surface modifier in order to suppress the immersion liquid from entering the end surface of the base material.

JP 2004-182796 A JP 2007-019465 A

  However, the fluorine-based surface modifier described in Patent Document 2 is actually a fluorine-containing compound (1,3-bis (3,3,3) having a fluorine-containing acyclic alkyl group and a reactive silyl group. -Trifluoropropyl) tetramethyldisilazane, 4-dimethyl (3,3,3-trifluoropropyl) siloxy-3-penten-2-one, isopropenoxy-3,3,3-trifluoropropyldimethylsilane and the like. However, it is considered that the water repellency necessary for suppressing the immersion of the immersion liquid cannot be imparted to the substrate. Therefore, a surface treatment method for a substrate for imparting high water repellency to the surface of the substrate is required.

The present invention has the following gist.
<1> A fluorine-based surface modifier containing a fluorine-containing compound (F) having a fluorine-containing cyclic saturated hydrocarbon group (F ^U ) and a reactive group (A ^U ) was applied to the substrate (S). A method for producing a surface-treated substrate that is reacted later.

<2> The fluorine-containing cyclic saturated hydrocarbon group (F ^U ) is represented by the following formula (1), the following formula (2), the following formula (3), the following formula (4), and the following formula (5). N-valent group obtained by removing n hydrogen atoms of a cyclic saturated hydrocarbon compound selected from the group consisting of compounds (where n represents an integer of 1 to 4), and 50% or more of the remaining hydrogen atoms The method for producing a surface-treated substrate according to <1>, wherein is a group (F ^U1 ) substituted with a fluorine atom.

When there is a residual hydrogen atom that is not substituted with a fluorine atom in the group (F ^U1 ), the residual hydrogen atom is a C 1-6 fluoroalkyl group or etheric oxygen which may contain an etheric oxygen atom. It may be substituted with a C1-C6 fluoroalkoxy group which may contain an atom.

<3> From the group represented by the following formula (F11 ^U ), the following formula (F12 ^U ), the following formula (F21 ^U ) and the following formula (F41 ^U ), wherein the fluorine-containing cyclic saturated hydrocarbon group (F ^U ) The method for producing a surface-treated substrate according to <1> or <2>, which is a group (F ^U11 ) selected from the group consisting of:

However, the symbol in a formula shows the following meaning.
R ¹ : an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
R ² and R ⁴ : each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
The fluorine atom in the group (F ^U11 ) is a C 1-6 perfluoroalkyl group which may contain an etheric oxygen atom or a C 1-6 perfluoroalkoxy group which may contain an etheric oxygen atom. May be substituted.

<4> substrate (S), a substrate having a reactive group ^{(A U)} reactive groups capable of reacting with ^{(B U)} a surface <1> - according to <3>, surface treated A manufacturing method of a base material.

<5> The method for producing a surface-treated substrate according to <4>, wherein the reactive group (A ^U ) is a reactive silyl group, and the reactive group (B ^U ) is a group having an active hydrogen atom. .
<6> The method for producing a surface-treated substrate according to <4> or <5>, wherein the reactive group (A ^U ) is a reactive silyl group, and the reactive group (B ^U ) is a hydroxy group. .

  <7> The method for producing a surface-treated substrate according to any one of <1> to <6>, wherein the surface-treated substrate is a substrate used in an immersion lithography method.

  According to the production method of the present invention, a substrate having a surface excellent in water and oil repellency can be easily produced.

In this specification, a compound represented by the formula (f1) is referred to as a compound (f1), and a group represented by the formula (F11 ^U ) is referred to as a group (F11 ^U ). Other compounds and other groups are described in the same manner. The symbols in the group are the same as above unless otherwise specified.

The fluorine-based surface modifier in the present invention includes a fluorine-containing compound (F) having a fluorine-containing cyclic saturated hydrocarbon group (F ^U ) and a reactive group (A ^U ).

The fluorine-containing cyclic saturated hydrocarbon group (F ^U ) in the fluorine-containing compound (F) in the present invention is a saturated group in which a fluorine atom is directly bonded to a carbon atom constituting the ring. The fluorinated cyclic saturated hydrocarbon group is preferably a monovalent group. The fluorine-containing cyclic saturated hydrocarbon group may be a fluorine-containing monocyclic saturated hydrocarbon group or a fluorine-containing polycyclic saturated hydrocarbon group. The fluorine-containing polycyclic saturated hydrocarbon group may be a fluorine-containing bridged cyclic saturated hydrocarbon group or a fluorine-containing condensed cyclic saturated hydrocarbon group.

The fluorine-containing cyclic saturated hydrocarbon group (F ^U ) is an m-valent group obtained by removing m hydrogen atoms from a cyclic saturated hydrocarbon compound (where m is an integer of 1 to 4. m is preferably 1). And a group in which 50% or more of the remaining hydrogen atoms are substituted with fluorine atoms is preferred.
80% or more of the remaining hydrogen atoms in the fluorine-containing cyclic saturated hydrocarbon group are preferably substituted with fluorine atoms, and all of them are particularly preferably substituted with fluorine atoms. When there is a residual hydrogen atom that is not substituted with a fluorine atom in the group, the residual hydrogen atom contains a C1-C6 fluoroalkyl group or an etheric oxygen atom that may contain an etheric oxygen atom. It may be substituted with a C1-C6 fluoroalkoxy group which may be

The fluorine-containing cyclic saturated hydrocarbon group (F ^U ) is a ring selected from the group consisting of the following compound (1), the following compound (2), the following compound (3), the following compound (4) and the following compound (5). A group (F ^U1 ) which is an n-valent group obtained by removing n hydrogen atoms of the formula saturated hydrocarbon compound and in which 50% or more of the remaining hydrogen atoms are substituted with fluorine atoms is more preferable.

80% or more of the remaining hydrogen atoms in the group (F ^U1 ) are preferably substituted with fluorine atoms, and all of them are particularly preferably substituted with fluorine atoms.
When the group (F ^U1 ) has a residual hydrogen atom that is not substituted with a fluorine atom, the residual hydrogen atom is a C 1-6 perfluoroalkyl group or etheric oxygen which may contain an etheric oxygen atom. The C1-C6 perfluoroalkoxy group which may contain an atom may be substituted.

n is preferably 1, and the group (F ^U1 ) is preferably a monovalent group.

The fluorine-containing cyclic saturated hydrocarbon group (F ^U ) is a group selected from the group consisting of the following group (F11 ^U ), the following group (F12 ^U ), the following group (F21 ^U ) and the following group (F41 ^U ) ( F ^U11 ) is particularly preferred.

The fluorine atom in the group (F ^U11 ) is a C 1-6 perfluoroalkyl group which may contain an etheric oxygen atom or a C 1-6 perfluoroalkoxy group which may contain an etheric oxygen atom. May be substituted.
R ¹ is preferably a methyl group or a trifluoromethyl group.
R ² and R ⁴ are preferably each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

The reactive group (A ^U ) in the present invention is preferably a reactive silyl group, an isocyanato group, a carboxy group, a hydroxy group, a mercapto group, or an amino group, from the viewpoint of reactivity and adhesion of the substrate (S). A reactive silyl group is particularly preferred.

The reactive silyl group is preferably the following group (S1 ^U ), the following group (S2 ^U ), the following group (S3 ^U ) or the following group (S4 ^U ), and particularly preferably the group (S1 ^U ).
_{^{-Si (X 1) 3-p}} (OX 1) p (S1 U),
_{^{-Si (X 21) 2 (-O}} -CX 22 = CX 23 -C (O) X 24) (S2 U),
_{^{-Si (X 31) 3-q}} (-O-CX 32 = CHX 33) q (S3 U).

However, the symbols in the formulas have the following meanings (the same applies hereinafter).
X ^1: a hydrocarbon group having 1 to 10 carbon atoms, three of X ¹ may be different it may be the same.
p: 1, 2 or 3.
X ^{21 is} a hydrocarbon group having 1 to 10 carbon atoms, and when q is 1, two X ^{21 s} may be the same or different.
X ²² and X ²³ are each independently a hydrocarbon group having 1 to 10 carbon atoms or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. When q is 2, two X ²² may be the same or different. When q, the two X ²³ may be the same or different.
X ²⁴ : a hydrocarbon group having 1 to 10 carbon atoms, a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms. When q is 2, two X ²⁴ may be the same or different.
X ³¹ : a hydrocarbon group having 1 to 10 carbon atoms. When q is 2, two X ³¹ may be the same or different.
X ³² and X ³³ are each independently a saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms. When q is 2, two X ³² may be the same or different. In the case of q, the two X ³³ may be the same or different.
q: 1, 2 or 3.

X ¹ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or an n-propyl group, and particularly preferably a methyl group. Also, preferably the three X ¹ are the same.
From the viewpoint of reactivity, p is preferably 2 or 3, and particularly preferably 3.

Specific examples of the group (S1 ^U ) include —Si (CH ₃ ) (OCH ₃ ) ₂ , —Si (CH ₂ CH ₃ ) (OCH ₂ CH ₃ ) ₂ , —Si (OCH ₃ ) ₃ , —Si ( OCH ₂ CH _{3) 3} and the like.

Specific examples of the group (S2 ^U ) include —Si (CH ₃ ) ₂ (—O—C (CH ₃ ) ═C (CH ₃ ) —C (O) CH ₃ ), —Si (CH ₃ ) ₂ ( _{-O-C (Cy) = C} (CH 3) -C (O) CH 3), - Si (CH 3) 2 (-O-C (CF 3) = CH-C (O) CF 3), - Si (CH ₃ ) ₂ (—O—C (—CH═CH ₂ ) ═C (CH ₃ ) —C (O) CH ₃ ), —Si (CH ₃ ) ₂ (—O—C (CH ₃ ) = C (CH ₃ ) —C (O) OCH ₃ ) (wherein Cy represents a cyclohexyl group; the same shall apply hereinafter).

Specific examples of the group (S3 ^U ) include —Si (CH ₃ ) ₂ (—O—C (CH ₃ ) ═CH ₂ ), —Si (CH ₃ ) ₂ (—O—C (Cy) ═CH _{2. ), - Si (CH 3)} 2 (-O-CH = CH 2), - Si (CH 3) 2 (-O-C (CH 3) = CHCH 3), - Si (CH 3) (- O- _{C (CH 3) = CHCH 3} ) 2 and the like.

In the fluorine-containing compound (F), the fluorine-containing cyclic saturated hydrocarbon group (F ^U ) and the reactive group (A ^U ) may be directly bonded or may be bonded via a linking group. The linking group is preferably a divalent organic group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 10 carbon atoms. -O-, -C (O)-, or -C (O) O- may be inserted between carbon atoms in the alkylene group. The carbon atom in the alkylene group may be substituted with a fluorine atom, a hydroxy group or a carboxy group.

  The fluorine-containing compound (F) is preferably the following compound (f1), particularly preferably the following compound (f11).

However, the symbols in the formulas have the following meanings (the same applies hereinafter).
Z ^m : a fluorine atom, or —W ^m —CH ₂ CH ₂ Si (R ^m ) ₃ , and the three Z ^m may be the same or different.
W ^m : a single bond, an etheric oxygen atom, an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, an alkylene group having an etheric oxygen atom having 2 to 6 carbon atoms, or 2 to 6 carbon atoms An oxyalkylene group having an etheric oxygen atom.
R ^m : an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and at least one R ^m is an alkoxy group having 1 to 6 carbon atoms.

W ^m is preferably a single bond, an alkylene group having 1 to 6 carbon atoms, or an oxyalkylene group having 1 to 6 carbon atoms, and a single bond, an alkylene group having 1 to 2 carbon atoms, or an oxyalkylene group having 1 to 2 carbon atoms. Particularly preferred.

-Si ^(R _m) 3 pieces of ^{R m} in _3, or 1 there 2 is an alkyl group having 1 to 6 carbon atoms is an alkoxy group having 1 to 6 carbon atoms, the number one carbon 1 Are preferably 1 to 6 alkyl groups and 2 are alkoxy groups having 1 to 6 carbon atoms, or 3 are alkoxy groups having 1 to 6 carbon atoms, and 1 is preferably from the viewpoint of reactivity. More preferably, it is an alkyl group having 1 to 6 and 2 is an alkoxy group having 1 to 6 carbon atoms, or 3 is an alkoxy group having 1 to 6 carbon atoms, and 3 is an alkoxy group having 1 to 6 carbon atoms. Particularly preferred is an alkoxy group.

Compound (f1) is a novel compound. The compound (f1) is obtained by reacting the following compound (of1) with H ₂ O to obtain the following compound (pf1), and then reacting the compound (pf1) with formaldehyde in the presence of a basic compound to produce the following compound ( qf1) is obtained, and then the compound (qf1) is reacted with CH ₂ ═CH—W ^m —Br to obtain the following compound (rf1). Next, the compound (rf1) is reacted with HSi (R ^m ) ₃ . It is preferable to manufacture by making it.

However, the symbol in a formula shows the following meaning.
Z ^o: a group corresponding to ^{Z p, Z o} corresponding to a fluorine atom is a fluorine atom, ^{Z o} is -COF corresponding to -H.
Z ^p: a group corresponding to ^{Z q, Z p} corresponding to the fluorine atom is a fluorine atom, ^{Z p} is -H corresponding to _-CH 2 OH.
Z ^q: a group corresponding to ^{Z r, Z q} corresponding to the fluorine atom is a fluorine ^{atom, Z q} is _-CH 2 OH corresponding to -W m _{-CH 2} = CH 2.
Z ^r: a group corresponding to ^{Z m, Z r} corresponding to a fluorine atom is a fluorine ^atom, corresponding to ^{_{-W m -CH 2 CH 2 Si (}} R m) 3 Z r is -W ^m - _{CH 2} = CH _2.

  Specific examples of the compound (F) include the following compounds.

  The fluorine-based surface modifier in the present invention may contain components other than the fluorine-containing compound (F) (also referred to as other components). Examples of other components include surface modifying components other than the fluorine-containing compound (F), reaction catalysts, and organic solvents.

  Examples of the surface modifying component other than the fluorine-containing compound (F) include silane coupling agents and silazanes.

  Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycid. Xylpropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylene Trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , Ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxy Silane, trimethylmethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimeth Silane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Specific examples of silazanes include hexamethyldisilazane, hexaethyldisilazane, bisethyldimethyldisilazane, and bispropyldimethyldisilazane.

  When the fluorine-type surface modifier in this invention contains surface modification components other than a fluorine-containing compound (F), 1-20 mass% of said surface modification components are included with respect to a fluorine-containing compound (F). preferable.

The reaction catalyst is a compound that catalyzes a reaction of the reactive group (A ^U ) in the fluorine-containing compound (F), or a reactive group (A ^{U when the} substrate (S) has a reactive group (B ^U ). as long as it is a compound which catalyzes the reaction between ^U) with the reactive group (B ^U), it is not particularly limited.
For example, examples of the catalyst when the reactive group (A ^U ) is a reactive silyl group and the reactive group (B ^U ) is a hydroxy group include organic acids such as carboxylic acid.
It is preferable that the fluorine-type surface modifier in this invention contains 1-20 mass% of reaction catalysts with respect to a fluorine-containing compound (F).

Since the fluorine-type surface modifier in this invention is apply | coated to a base material (S), it is desirable to prepare in liquid state and it is preferable that an organic solvent is included.
An organic solvent will not be specifically limited if it is a solvent with high compatibility with a fluorine-containing compound (F). The organic solvent may be a fluorinated organic solvent or a non-fluorinated organic solvent.

Specific examples of the fluorine-based organic solvent include hydrochlorofluorocarbons such as CCl ₂ FCH ₃ , CF ₃ CF ₂ CHCl ₂ , and CClF ₂ CF ₂ CHClF; CF ₃ CHFCHFCF ₂ CF ₃ , CF ₃ (CF ₂ ) ₅ H, Hydrofluorocarbons such as CF ₃ (CF ₂ ) ₃ C ₂ H ₅ , CF ₃ (CF ₂ ) ₅ C ₂ H ₅ , CF ₃ (CF ₂ ) ₇ C ₂ H ₅ ; 1,3-bis (trifluoromethyl) ) Hydrofluorobenzenes such as benzene and metaxylene hexafluoride; Hydrofluoroketones; Hydrofluoroalkylbenzenes; CF ₃ CF ₂ CF ₂ CF ₂ OCH ₃ , (CF ₃ ) ₂ CFCF (CF ₃ ) CF ₂ OCH ₃ , CF ₃ CH ₂ OCF ₂ CHF _{2 and} other hydrofluoroethers And hydrofluoroalcohols such as CHF ₂ CF ₂ CH ₂ OH.

  Specific examples of the non-fluorinated organic solvent include methyl alcohol, ethyl alcohol, diacetone alcohol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethylbutanol, pentanol, and hexanol. , Alcohols such as heptanol, acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, ketones such as N-methylpyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, Propylene glycol monoethyl ether acetate, carbitol acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, butyric acid Ethyl, propyl butyrate, methyl isobutyl ketone, ethyl acetate, 2-ethoxyethyl acetate, isoamyl acetate, methyl lactate, ethyl lactate and other esters, aromatic hydrocarbons such as toluene and xylene, propylene glycol monomethyl ether, propylene glycol methyl ether Glycol mono or dialkyl ethers such as acetate, propylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide and the like It is done.

  The fluorine-based surface modifier in the present invention is a fluorine-containing compound (F) (when the fluorine-based surface modifier contains a surface modifying component other than the fluorine-containing compound (F), The organic solvent is preferably contained in an amount of 100 to 100,000% by mass relative to the total mass of the surface modifying component.

Substrate in the present invention (S) _is a by SiO 2, Si, SiON, SiN , p-Si, α-Si, W, W-Si, Al, Cu, substrates made of an inorganic material such as Al-Si It may be a substrate made of an organic material. Moreover, the base material (S) may be surface-treated with a surface modifying component other than the fluorine-containing compound (F).
Specific examples of the substrate (S) include glass, silicon wafer, and resin.

Substrate (S) is a fluorine-containing compound (F) and the adhesion of the terms, the reactive group (A ^U) reactive groups capable of reacting with (B ^U) a substrate having a surface is preferable.
The reactive group (B ^U ) is appropriately selected according to the type of the reactive group (A ^U ). For example, when the reactive group (A ^U ) is a reactive silyl group, the reactive group (B ^U ) is preferably a group having an active hydrogen atom, more preferably a hydroxy group, a mercapto group or an amino group, Is particularly preferred.

  In the production method of the present invention, the fluorine-based surface modifier is applied to the substrate (S) and then reacted.

  As a coating method of the fluorine-based surface modifier in the present invention, a method of applying a fluorine-based surface modifier to the surface of the substrate (S), a fluorine-based surface modifier on the surface of the substrate (S) The method of spraying and the method of immersing a base material (S) in a fluorine-type surface modifier are mentioned.

  The coating method is not particularly limited, and examples thereof include a roll coating method, a casting method, a dip method, a spin coating method, a water casting method, and a die coating method.

When the fluorine-based surface modifier contains an organic solvent, it is preferable to dry the substrate (S) after coating the fluorine-based surface modifier on the substrate (S).
However, “drying” means an operation of volatilizing and distilling the organic solvent in the fluorine-based surface modifier applied to the substrate (S). Drying conditions are appropriately selected depending on the type of organic solvent and the like. For example, the conditions which hold | maintain a base material (S) at 100 degreeC or more for 1 minute-1 hour are mentioned.
In addition, in the application of the fluorine-based surface modifier, the fluorine-based surface modifier may be applied to the entire surface of the substrate (S), and a specific portion (end face, surface) of the surface of the substrate (S). It may be applied to the outer periphery, etc.).

The “reaction” in the production method of the present invention means reacting the reactive group (A ^U ) in the fluorine-containing compound (F). When the substrate (S) has a reactive group (B ^U) on the surface, a fluorine-containing compound (F) reactive groups in (A ^U), the substrate (S) reactive groups on the surface (B ^U )) is usually meant to react. The reaction usually involves the formation of a chemical bond between the fluorine-containing compound (F) and the substrate (S).
The reaction conditions can be appropriately selected according to the type of the reactive group (A ^U ) in the fluorine-containing compound (F). When the reactive group (A ^U ) is a reactive silyl group, the reaction may be carried out at 50 to 200 ° C. for 30 seconds to 1 hour.
In the production method of the present invention, “drying” and “reaction” may be performed in the same step.

  According to the production method of the present invention, a base material having high water and oil repellency on the surface can be produced. The reason is not necessarily clear, but the fluorine-containing compound (F) in the present invention is a reactive compound having a bulky structure derived from a fluorine-containing ring structure, and a reactive compound having an acyclic fluorine-containing structure. It is considered that the fluorine-containing portion in the compound is easily oriented to the outermost surface when applied to the substrate surface to form a coating film.

The substrate surface-treated by the production method of the present invention is used for window glass, lenses (glass lenses, optical lenses, etc.), light emitting diodes, displays (PDP, LCD, FED, organic EL, etc.), semiconductor members, and the like. Applicable to. Especially, since the said base material is provided with high water and oil repellency, it is preferable to use it as a base material used for the immersion lithography method. The substrate is not particularly _{limited, Si, SiO 2, SiON,} SiN, p-Si, α-Si, W, W-Si, a substrate selected from the group consisting of Al and Al-Si and the like.

  By using the substrate surface-treated by the production method of the present invention for the immersion lithography method, the immersion liquid is prevented from entering the end surface of the substrate. Therefore, contamination between the end surface / back surface of the substrate and the exposure apparatus due to the immersion liquid can be suppressed. Therefore, the immersion lithography method can be stably carried out by the manufacturing method of the present invention.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
In Examples, tetramethylsilane is referred to as TMS, and CF ₂ ClCF ₂ CHFCl (dichloropentafluoropropane) is referred to as R225.

[Example 1] Production Example of Compound (f1 ¹ ) The following compound (of1 ¹ ) (27.46 g), NaF (3.78) and acetone (100 mL) were placed in a flask maintained at 0 ° C. and stirred. Next, water (1.14g) was dripped at the flask, and the inside of a flask was fully stirred. The flask content liquid was purified by sublimation to obtain the following compound (pf1 ¹ ) (22.01 g).

To a mixture of the compound (pf1 ¹ ) (2.03 g) and dimethyl sulfoxide (50 mL) were added potassium hydroxide (1.00 g) and a formalin aqueous solution (20 mL), and the mixture was allowed to react at 75 ° C. for 6.5 hours. After completion of the reaction, the reaction solution was extracted into R225 (40 mL), and further R225 was distilled off to obtain the following compound (qf1 ¹ ) (1.58 g).

A compound (qf1 ¹ ) (110 g) obtained in the same manner and dimethyl sulfoxide (550 g) were placed in a flask (internal volume 1 L) and stirred. Next, 28 mass% potassium hydroxide aqueous solution (153 g) was dripped at the flask over 30 minutes. After completion of the dropping, the inside of the flask was stirred at 25 ° C. for 2 hours. Next, CH ₂ = CHCH ₂ CH ₂ Br (74.5 g) was added dropwise to the flask over 30 minutes, and the mixture was stirred at 25 ° C for 19 hours.

Subsequently, a saturated aqueous sodium chloride solution (500 mL) and R225 (500 mL) were added to the flask for liquid separation. The recovered organic layer was washed with a saturated aqueous sodium chloride solution (500 mL), dried over magnesium sulfate, and then evaporated to give the following compound (rf1 ¹ ) (111.1 g).

To a flask (internal volume: 500 mL), a mixture of the compound (rf1 ¹ ) (50 g) and tetrahydrofuran (240 g) and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex were added in an amount of 0. A 3% by weight xylene solution (13.8 g) was added. Next, HSi (OCH ₃ ) ₃ (27 g) was added dropwise to the flask over 10 minutes, and the mixture was heated at 60 ° C. for 2 hours. After the solvent in the flask was distilled off, the contents of the flask were purified by a column chromatography method (developing solvent: hexane / ethyl acetate = 10: 1) to obtain the following compound (f1 ¹ ) (55 g).

The NMR data of the compound (f1 ¹ ) are shown below.
¹ H-NMR (300.4 MHz, CDCl ₃ , TMS) δ (ppm): 0.69 (m, 2H), 1.50 (m, 2H), 1.70 (m, 2H), 2.24 ( m, 2H), 3.58 (s, 9H).
¹⁹ F-NMR (282.7 MHz, CDCl ₃ , CFCl ₃ ) δ (ppm): −113.5 (6F), −121.2 (6F), −219.1 (3F).

[Example 2] Production example of fluorine-based surface modifier [Example 2-1] Production example of fluorine-based surface modifier (1) The compound (f1 ¹ ) contains 3.0% by mass, and acetic acid is reduced to 0. A diisoamyl ether solution containing 4% by mass was prepared. The solution was filtered through a 0.2 μm pore size filter (manufactured by PTFE) to obtain a fluorine-based surface modifier (1).
[Example 2-2] Production example of fluorine-based surface modifier (2) A propylene glycol monomethyl ether acetate solution containing 3.0% by mass of compound (f1 ¹ ) and 0.4% by mass of acetic acid was prepared. . The solution was filtered through a filter (made of PTFE) having a pore size of 0.2 μm to obtain a fluorine-based surface modifier (2).

[Example 4] Production example of surface-treated base material Fluorine-based surface modifier (1) was spin-coated on the surface of a silicon substrate. Next, the silicon substrate was heated at 110 ° C. for 60 seconds for reaction and drying, and the surface of the silicon substrate was surface-treated with the fluorine-based surface modifier (1).
Next, the static contact angle, the falling angle, and the receding angle with respect to the water on the surface treated with the fluorine-based surface modifier (1) were measured. In addition, the sliding angle measured by the sliding method is described as the falling angle, and the receding contact angle is denoted as the receding angle.

  Further, the surface treatment of the silicon substrate is performed in the same manner except that the fluorine-based surface modifier (2) is used in place of the fluorine-based surface modifier (1), and the contact angle, the falling angle, and the receding angle with respect to water. Was measured. The results are summarized in Table 1 (units of static contact angle, rolling angle, and receding angle are angles (°), respectively, where the sliding angle and receding angle were measured using the sliding method). In addition, the numerical value shown as a comparative example is a static contact angle, a falling angle, and a receding angle of an untreated silicon substrate.

  As is clear from the above results, it can be seen that high water repellency can be imparted to the substrate surface by using the fluorine-based surface modifier of the present invention.

  According to the present invention, a substrate having a surface excellent in high water and oil repellency can be easily produced. According to the manufacturing method of the present invention, it is possible to stably carry out the immersion lithography method without fear of contamination of the base material and the exposure apparatus by the immersion liquid.

Claims (7)

After the fluorine-based surface modifier containing the fluorine-containing compound (F) having the fluorine-containing cyclic saturated hydrocarbon group (F ^U ) and the reactive group (A ^U ) is applied to the substrate (S), the reaction is performed. A method for producing a surface-treated substrate. The fluorine-containing cyclic saturated hydrocarbon group (F ^U ) is composed of compounds represented by the following formula (1), the following formula (2), the following formula (3), the following formula (4), and the following formula (5). An n-valent group obtained by removing n hydrogen atoms of a cyclic saturated hydrocarbon compound selected from the group (where n represents an integer of 1 to 4), and 50% or more of the remaining hydrogen atoms are fluorine atoms. The method for producing a surface-treated substrate according to claim 1, which is a group (F ^U1 ) substituted on.

When there is a residual hydrogen atom that is not substituted with a fluorine atom in the group (F ^U1 ), the residual hydrogen atom is a C 1-6 fluoroalkyl group or etheric oxygen which may contain an etheric oxygen atom. It may be substituted with a C1-C6 fluoroalkoxy group which may contain an atom. The fluorine-containing cyclic saturated hydrocarbon group (F ^U ) is selected from the group consisting of groups represented by the following formula (F11 ^U ), the following formula (F12 ^U ), the following formula (F21 ^U ), and the following formula (F41 ^U ). The manufacturing method of the surface-treated base material of Claim 1 or 2 which is group (F ^U11 ) chosen.

However, the symbol in a formula shows the following meaning.
R ¹ : an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
R ² and R ⁴ : each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.
The fluorine atom in the group (F ^U11 ) is a C 1-6 perfluoroalkyl group which may contain an etheric oxygen atom or a C 1-6 perfluoroalkoxy group which may contain an etheric oxygen atom. May be substituted. Substrate (S) is, according to claims 1 to 3 reactive groups capable of reacting with the reactive group (A ^U) and (B ^U) is a substrate having a surface, the production of surface-treated substrate Method. The method for producing a surface-treated substrate according to claim 4, wherein the reactive group (A ^U ) is a reactive silyl group, and the reactive group (B ^U ) is a group having an active hydrogen atom. The method for producing a surface-treated substrate according to claim 4 or 5, wherein the reactive group (A ^U ) is a reactive silyl group and the reactive group (B ^U ) is a hydroxy group.   The method for producing a surface-treated substrate according to any one of claims 1 to 6, wherein the surface-treated substrate is a substrate used for an immersion lithography method.