KR20070018058A - Liquid for immersion exposure and immersion exposure method - Google Patents

Abstract

The present invention relates to a liquid immersion exposure liquid and a liquid immersion exposure method using the liquid, which have a large refractive index in the liquid immersion exposure method and which can prevent elution or dissolution of a photoresist film or its upper layer components and can suppress defects in forming a resist pattern. It is for the purpose of providing. The liquid of the present invention is a liquid used in an immersion exposure apparatus or an immersion exposure method for exposing through a liquid filled between a lens of a projection optical system and a substrate, and the liquid is a liquid in a temperature range in which the immersion exposure apparatus operates, and an alicyclic type It is a cyclic hydrocarbon compound which contains a hydrocarbon compound or a silicon atom in ring structure.

Liquid for liquid immersion exposure, liquid immersion exposure liquid composition, photoresist film

Description

Liquid for liquid immersion exposure and liquid immersion exposure method {LIQUID FOR IMMERSION EXPOSURE AND IMMERSION EXPOSURE METHOD}

The present invention relates to a liquid for liquid immersion exposure and a liquid immersion exposure method, and more particularly, to a liquid and a method thereof, as well as a method for producing the liquid for liquid immersion exposure, an evaluation method as a liquid for liquid immersion exposure, and a novel liquid composition.

When manufacturing a semiconductor element or the like, a stepper-type or step-and-scan projection exposure apparatus is used which transfers a pattern of a reticle as a photomask to each shot region on a wafer to which photoresist is applied via a projection optical system.

The theoretical limit value of the resolution of the projection optical system provided in the projection exposure apparatus is shorter as the exposure wavelength to be used and the numerical aperture of the projection optical system is larger. Therefore, with the miniaturization of integrated circuits, the exposure wavelength which is the wavelength of the radiation used by a projection exposure apparatus is shortening year by year, and the numerical aperture of a projection optical system is also increasing.

In addition, when performing exposure, the depth of focus is also important as is the resolution. The theoretical limit values of the resolution R and the depth of focus δ are each represented by the following equation.

R = k1 λ / NA

δ = k ² .λ / NA ²

Here, lambda is the exposure wavelength, k1 and k2 are the process coefficients, NA is the numerical aperture of the projection optical system, and when the refractive index of air is 1, it is defined by the following formula ii '. In other words, when the same resolution R is obtained, a large focal depth δ can be obtained by using radiation having a short wavelength.

NA = sinθ (θ = maximum incident angle of exposure light to the resist surface)

As described above, until now, the shortening of the exposure light source and the increase of the numerical aperture have made it possible to meet the demand for miniaturization of integrated circuits, and now 1L1S (1: 1 line) using an ArF excimer laser (wavelength 193 nm) as the exposure light source. And space) Mass production of a half pitch 90 nm node is examined. However, for the next generation half pitch 65 nm node or 45 nm node, which has been further refined, it is said that it is difficult to achieve only by using ArF excimer laser. Thus, the use of the short wavelength light source has been studied, such as for those of the next generation technology, F ₂ excimer laser (wavelength: 157 ㎚), EUV (wavelength 13 ㎚). However, since the use of these light sources has high technical difficulty, they are still in a difficult situation.

By the way, in the above exposure technique, a photoresist film is formed on the exposed wafer surface, and the pattern is transferred to the photoresist film. In the conventional projection exposure apparatus, the space in which the wafer is placed is filled with air or nitrogen having a refractive index of one. At this time, when the space between the wafer and the lens of the projection exposure apparatus is filled with a medium having a refractive index of n, it is reported that the theoretical limit values of the resolution R and the depth of focus δ are expressed by the following equation.

R = k1 (λ / n) / NA

δ = k ^{2 n 2} / NA ²

Here, NA is not an actual numerical aperture of the projection optical system, but means a constant defined by Equation ii '(exactly, the numerical aperture NA' of the projection optical system is NA '= nsinθ (n is the same definition as above). Displayed)

The above equation is a theory that it is theoretically possible to fill the liquid having a refractive index n between the lens of the projection exposure apparatus and the wafer and set an appropriate optical system so that the limit value and the depth of focus can be increased to 1 / n times n times, respectively. It means. For example, in the ArF process, when water is used as the medium, the refractive index n in the water of light having a wavelength of 193 nm is 1.44. Therefore, the resolution R is 69.4% (R = It is theoretically possible to design an optical system such that k1 · (λ / 1.44) / NA and the depth of focus are 144% (δ = k2 · 1.44λ / NA ² ).

The method of projecting exposure by shortening the effective wavelength of the radiation for exposure and transferring a finer pattern is called immersion exposure, and is considered to be an essential technique for the future miniaturization of lithography, especially lithography on the order of tens of nm. And its projection exposure apparatus are also known (Japanese Patent Laid-Open No. 11-176727).

Conventionally, in the liquid immersion exposure method, as a liquid filled between the lens of the projection optical system and the substrate, the use of fluorine-based inert liquid or the like is not used because of its high transparency at 157 nm in an ArF excimer laser and 157 nm in an F ₂ excimer laser. Has been reviewed.

Pure water is easy to obtain from semiconductor manufacturing plants, and environmentally friendly. Moreover, since temperature adjustment is easy and thermal expansion of the board | substrate is prevented by the heat which generate | occur | produces during exposure, it is employ | adopted as a liquid of the immersion liquid for ArF (refer international publication WO99 / 49504), and is 65 nm half pitch node. The adoption for the mass production of the device is certain.

On the other hand, a liquid in which methyl alcohol or the like is added as an additive for reducing the surface tension of pure water and increasing the interfacial activity is also known (see Japanese Patent Laid-Open No. Hei 10-303114).

However, by using pure water, water may penetrate into the photoresist film, resulting in deterioration in shape such that the cross-sectional shape of the photoresist pattern becomes a T-top shape, or the resolution may decrease. In addition, water-soluble components such as photoacid generators, basic additives, and acids generated by exposure to the photoresist are eluted in water, resulting in deterioration of shapes such as T-top shapes, deterioration in resolution, depth of focus, and bridge defects. This may occur, or defects may occur in the pattern after development, and the lens surface may be contaminated. In addition, elution of these components into the liquid causes contamination of the liquid at the same time, which makes it difficult to reuse the liquid. For this reason, a cumbersome purification process is required frequently.

For this reason, there is a method of forming an upper layer film on the photoresist film for the purpose of blocking the photoresist film and water, but there is a case where sufficient permeability to exposure or intermixing with the photoresist film is not sufficient. The number of processes is complicated. In addition, it has been reported that CaF _{2, which} has been conventionally used as a lens material, is eroded by water (NIKKEI MICRODEVICE, April 2004, p. 77), which causes a problem that a coating material for coating the lens surface is required. .

On the other hand, as indicated by Equation (iii), since the limit of resolution is about 1.44 times that of ArF dry exposure, it is predicted that its use is difficult in the next-generation technology in which the miniaturization is more advanced, especially in the half pitch of 45 nm or less.

As described above, in the next-generation liquid immersion lithography in which miniaturization has been further progressed, a liquid having a higher refractive index than pure water at an exposure wavelength (for example, wavelength 193 nm, etc.) and a high transmittance to these wavelengths is required. At the same time, the liquid is required to be a liquid which does not adversely affect the photoresist film, such as dissolution of additives from the photoresist film, dissolution of the resist film, and deterioration of the pattern, and which does not corrode the lens. At the same time, the introduction of polarized light as exposure light has been studied by the high NA by the introduction of liquid immersion exposure, and the liquid is a liquid which does not bend the direction of polarization due to properties such as opticality in addition to the above-described requirements. It is expected.

As a method of achieving this object, for example, attempts have been made to increase the refractive index by dissolving various salts in water (Proc. SPIE Vol. 5377 (2004) p.273). However, this approach is not only difficult to control the concentration of salts, but also has problems such as development defects due to elution of water-soluble components and contamination of lenses, as well as water.

On the other hand, fluorine-based inert liquids such as perfluoropolyethers, which have been studied for F ₂ exposure, have a low refractive index at 193 nm, for example, and thus are difficult to use at the above wavelengths. Further, organic bromide and iodide, which is conventionally known as a liquid immersion exposure liquid for microscopes at a wavelength of 589 nm for high refractive index, deteriorates the transmittance at 193 nm, for example, and is poor in stability to the photoresist film.

<Start of invention>

Problems to be Solved by the Invention

SUMMARY OF THE INVENTION The present invention has been made to address such a problem, and has a refractive index greater than that of pure water in the immersion exposure method, has excellent transmittance at the immersion exposure wavelength, and prevents dissolution or dissolution of a photoresist film or its upper layer component (especially hydrophilic component). By preventing and suppressing defects generated during the formation of a resist pattern without eroding the lens, when used as a liquid for immersion exposure, deterioration of the pattern shape can be suppressed, and a pattern having a better resolution and depth of focus can be formed. It is an object of the present invention to provide a liquid for liquid immersion exposure, and a liquid immersion exposure method using the liquid, in which liquid is easily reused and purified.

Moreover, it aims at providing not only the said liquid immersion exposure liquid and the liquid immersion exposure method, but also the manufacturing method of the said liquid immersion exposure liquid, the evaluation method as a liquid for immersion exposure, and a novel liquid composition.

Means for solving the problem

In order to solve the said subject, having the high transmittance | permeability in the exposure wavelength which can be used for this objective, and having sufficiently high refractive index compared with water was an essential condition required for the liquid for immersion exposure. On the other hand, it is generally known that the refractive index of the ultraviolet region of the liquid depends on the polarization of the molecules constituting the liquid. As a method of increasing the polarization rate, for example, introducing an element having mobile n electrons such as sulfur, bromine and iodine into a molecule and a carbon-carbon double bond having a relatively mobile π electron, carbon-carbon 3 It is generally effective to introduce heavy bonds, especially aromatic rings. However, compounds containing these elemental and molecular structures generally cannot be used for this purpose because they have strong absorption in an extra-violet region such as 193 nm. On the other hand, examples of the compound having a low absorption in the extra-violet region include unsubstituted hydrocarbon compounds, cyanohydrocarbon compounds, fluorinated hydrocarbon compounds, sulfonic acid ester compounds and some alcohols, and these compounds generally have a higher refractive index than water. However, his refractive index is not significantly different from the current water.

On the other hand, the following formula (Lorentz-Lorenz's formula) has been proposed as a more accurate theoretical formula for the refractive index of liquids, and the results have been reported that the refractive index n of benzene can be accurately predicted using the following formula (J. Phy. Chem. A., Vol. 103, N0. 42, 1999 p 8447].

n = (1 + 4πNα ^eff ) 0.5

In the above formula, N represents the number of molecules in a unit volume, and the smaller the partial molar volume, the larger the value.

From the above chemical formula, it is predicted that the refractive index is increased by increasing N even when α cannot be increased by the introduction of a superabsorbing functional group. As a result of various studies on the molecular structure of the liquid with reference to the above, a liquid containing a dense alicyclic hydrocarbon or silicon of the present invention having a dense structure and having a cyclic hydrocarbon backbone not only makes transparency and refractive index compatible? However, when used as a liquid for liquid immersion exposure, it prevents the elution or dissolution of the photoresist film or its upper layer film component (particularly the hydrophilic component), and solves problems such as defects in the formation of a resist pattern, erosion of the lens, and the like. The present inventors have found that a pattern having a better depth can be formed, and have completed the present invention.

That is, the liquid immersion exposure liquid of the present invention is used in an immersion exposure apparatus or an immersion exposure method for exposing through a liquid filled between a lens of a projection optical system and a substrate, wherein the liquid is a liquid in a temperature range in which the immersion exposure apparatus operates. And a cyclic hydrocarbon compound containing an alicyclic hydrocarbon compound or a silicon atom in a ring structure.

In particular, the cyclic hydrocarbon compound containing an alicyclic hydrocarbon compound or a silicon atom in the ring structure has a radiation transmittance of 70% or more and a refractive index of D line of 1.4 or more, preferably 1.4 to 2.0, per 1 mm of optical path length at a wavelength of 193 nm. It is characterized by that.

The liquid immersion exposure method of the present invention is a liquid immersion exposure method for illuminating a mask with an exposure beam and exposing the substrate with an exposure beam through a liquid filled between the lens of the projection optical system and the substrate, wherein the liquid is the liquid for liquid immersion exposure described above. It features.

Effect of the Invention

The liquid immersion lithography method of the present invention uses a cyclic hydrocarbon compound having a high hydrophobicity and a high refractive index alicyclic hydrocarbon compound or a silicon atom in a ring structure as an immersion lithography liquid, thereby using a photoresist film or an upper layer film component thereof. In particular, it is possible to prevent the dissolution or dissolution of the hydrophilic component, to solve the problem of defects in the formation of the resist pattern and the erosion of the lens, and when used as a liquid for immersion exposure, to suppress the deterioration of the pattern shape and to improve the resolution and the depth of focus. It is possible.

Best Mode for Carrying Out the Invention

It is preferable that the cyclic hydrocarbon compound which contains the alicyclic hydrocarbon compound or silicon atom which can be used as a liquid for immersion exposure in a ring structure is respectively a cyclic saturated hydrocarbon compound which contains an alicyclic saturated hydrocarbon compound or a silicon atom in a ring structure. When an unsaturated bond exists in a hydrocarbon compound, an exposure beam will become easy to be absorbed by the liquid for liquid immersion exposure.

The cyclic hydrocarbon compound which contains the alicyclic hydrocarbon compound or silicon atom which can be used as a liquid for immersion exposure is demonstrated by following General formula (1-1)-1-9.

In Formula 1-1, R ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine substituted hydrocarbon group having 1 to 10 carbon atoms, and -Si (R ⁹ ) represents a ₃ group or a -SO ₃ R ¹⁰ group, n1, n2 each independently represent an integer of 1 to 3, a represents an integer of 0 to 10, and when a plurality of R ¹ are present, these R ¹ is It may be the same or different, two or more R ¹ may be bonded to each other to form a ring structure, and R ⁹ and R ¹⁰ represent an alkyl group having 1 to 10 carbon atoms.

As a C1-C10 aliphatic hydrocarbon group in R <^1> , a methyl group, an ethyl group, n-propyl group, etc. are mentioned. Examples of the two or more R ¹ 's bonded to each other to form a ring structure include a cyclopentyl group, a cyclohexyl group, and the like. As a C3-C14 alicyclic hydrocarbon group, a cyclohexyl group, a norbornyl group, etc. are mentioned. Examples of the fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms include trifluoromethyl group and pentafluoroethyl group. -Si (R ⁹⁾ R ¹⁰ as constituting R ⁹ and -SO ₃ R ¹⁰ groups that comprise ₃ group, an alkyl group having 1 to 10 carbon atoms, the alkyl groups there may be mentioned methyl group and ethyl group and the like.

Substituents for R ^{1 in} the general formula (1-1) include an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a fluorine atom, and 1 carbon atom in view of excellent radiation transmittance of 193 nm. Preference is given to fluorine substituted saturated hydrocarbon groups of 10 to 10.

Among the substituents, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms have a higher refractive index, less interaction with the resist, and a defect due to elution of the water-soluble component in the resist. Particularly preferred is the formation and erosion of the lens material since it is unlikely to occur.

Further, preferred n1 and n2 are 1 to 3, particularly preferred n1 and n2 are 1 or 2, and preferred a is 0, 1 or 2. Especially as a, when it is 0, since refractive index in 193 nm becomes high, it is especially preferable.

The specific example of the preferable alicyclic saturated hydrocarbon compound represented by General formula (1-1) is shown below. In addition, in this specification, the hydrogen atom couple | bonded with the carbon atom which forms the ring in an alicyclic saturated hydrocarbon compound has abbreviate | omitted description.

The specific example of the preferable cyano group containing compound represented by General formula (1-1) is shown below.

The specific example of the preferable fluorine atom containing compound represented by General formula (1-1) is shown below.

The specific example of the preferable fluorine-substituted saturated hydrocarbon compound represented by General formula (1-1) is shown below.

Among the preferred compounds represented by the general formula (1-1), alicyclic saturated hydrocarbon compounds are preferred, and among these, particularly preferred compounds include compounds represented by the following general formula (2-1).

In Formula 2-1, R ¹ and a are the same as R ¹ a and of the formula 1-1.

As a specific example in General formula (2-1), (1-1-16), (1-1-19), (1-1-20), (1-1-21), (1-1-34), The compound quoted as (1-1-35), (1-1-36), (1-1-37), (1-1-38), and (1-1-39) is mentioned.

Among these, the compound which does not have a substituent is preferable, for example, since the refractive index in 193 nm becomes high, and cis-decalin and trans-decalin are mentioned as an especially preferable example in general formula (2-1).

In Formula 1-2, A represents a methylene group which may be substituted with a single bond or an alkyl group having 1 to 10 carbon atoms or an alkylene group having 2 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms, and R ² is carbon number Aliphatic hydrocarbon group of 1 to 10, alicyclic hydrocarbon group of 3 to 14 carbon atoms, cyano group, hydroxyl group, fluorine atom, fluorine substituted hydrocarbon group of 1 to 10 carbon atoms, -Si (R ⁹ ) ₃ group or -SO ₃ R ¹⁰ Represents a group, R ⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine substituted alkyl group having 1 to 10 carbon atoms, or a -Si (R ⁹ ) ₃ group, and n ₃ represents a group of 2 to 4 An integer is shown, n4 represents the integer of 1-3, b represents the integer of 0-6, and when ^two or more R <^2> or R <^7> exists, these R <^2> may be same or different and two or more R's ² combine with each other to form a ring structure. R ⁹ and R ¹⁰ may be an alkyl group having 1 to 10 carbon atoms.

As an methylene group which may be substituted by the C1-C10 alkyl group in A, or the same C2-C14 alkylene group, an ethylene group, n-propylene group, etc. are mentioned.

R ² is the same as R ¹ in Formula 1-1.

Substituents for R ^{2 in} the chemical formulas 1-2 include an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a fluorine atom and 1 carbon atom in view of excellent radiation transmittance of 193 nm. Preference is given to fluorine substituted saturated hydrocarbon groups of 10 to 10.

Among the substituents, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable for the same reasons as R ¹ in the general formula (1-1).

Preferred n3 is 2 to 4, particularly preferably 2 or 3, preferred n4 is 1 to 3, particularly preferably 1 or 2, and preferred b is 0, 1 or 2. As b, especially 0 is preferable because the refractive index at 193 nm becomes high, for example. Specific examples of preferable Formula 1-2 are shown below.

Particularly preferred examples of the formula (1-2) include 1,1,1-tricycloheptyl methane and 1,1,1-tricyclopentyl methane.

In Formula 1-3, R ³ and R ⁴ are an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine substituted hydrocarbon group having 1 to 10 carbon atoms,- When a Si (R ⁹ ) ₃ group or a -SO ₃ R ¹⁰ group is present and a plurality of R ³ and R ⁴ are present, respectively, these R ³ and R ⁴ may be the same or different, respectively, and two or more R ³ and R ⁴ may be each alone or in combination with each other to form a ring structure, n5 and n6 represent an integer of 1 to 3, c and d represent an integer of 0 to 8, R ⁹ and R ¹⁰ is a carbon number from 1 to An alkyl group of 10 is shown.

R ³ and R ⁴ are the same as R ¹ of Formula 1-1.

As a substituent of R <^3> and R <^4> in Formula 1-3, a C1-C10 aliphatic saturated hydrocarbon group, a C3-C14 alicyclic saturated hydrocarbon group, a cyano group, and a fluorine atom from a viewpoint of the excellent 193 nm radiation transmittance And fluorine-substituted saturated hydrocarbon groups having 1 to 10 carbon atoms.

Among the substituents, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable for the same reasons as R ¹ in the general formula (1-1).

Preferred n5 and n6 are 1 to 3, particularly preferably 1 or 2, and c and d are 0, 1 or 2. It is especially preferable that both of c and d are 0 because the refractive index at 193 nm becomes high, for example. The specific example of preferable compound 1-3 is shown below.

As a preferable example in General formula 1-3, spiro [5.5] undecane is mentioned.

In (a), (b) and (c) in the general formula (1-4), B represents a methylene group or an ethylene group, R ⁵ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms, -Si (R ⁹⁾ ₃ group, or -SO ₃ R ¹⁰ group represents, when a plurality of R ⁵ is present, these R ⁵ are the same or different Or two or more R ⁵ may be bonded to each other to form a ring structure, e represents an integer of 0 to 10, n7 represents an integer of 1 to 3, and R ⁹ and R ¹⁰ represent 1 to C An alkyl group of 10 is shown.

R ⁵ is the same as R ¹ in Formula 1-1.

Substituents for R ^{5 in} the general formula (1-4) include an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a fluorine atom, and 1 carbon atom in view of excellent radiation transmittance of 193 nm. The fluorine substituted saturated hydrocarbon group of 10 to 10 is preferable.

Among the substituents, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable for the same reason as R ¹ of the general formula (1-1).

Preferred e is 0, 1 or 2, n7 is 1 to 3, particularly preferably 1 or 2. Especially when e is 0, since the refractive index at 193 nm becomes high, for example, it is preferable. Examples of preferable compound 1-4 are shown below.

Preferred compounds of the general formula (1-4) include compounds represented by the general formulas (2-2) and (2-2 ').

In the formula 2-2, 2-2 ', R ⁵ is the same as R ⁵ in the formula 1-4, a preferred i is 0, 1 or 2; It is particularly preferable that i is 0 for the same reasons as a in the general formula (1-1).

As a specific example of preferable compound 2-2, 2-2 ', the compound of said (1-4-1)-(1-4-6) is mentioned.

As an especially preferable example, exo-tetrahydrodicyclopentadiene is mentioned.

In Formula 1-5, R ⁶ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine substituted hydrocarbon group having 1 to 10 carbon atoms, -Si (R ⁹ ) represents a ₃ group or a -SO ₃ R ¹⁰ group, f represents an integer of 0 to 10, and when a plurality of R ⁶ are present, these R ⁶ may be the same or different, R ⁹ and R ¹⁰ is carbon number 1 To alkyl group of 10.

R ⁶ is the same as R ¹ in Formula 1-1.

Substituents for R ^{6 in} the general formula (1-5) include an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a fluorine atom and 1 carbon atom in view of excellent radiation transmittance of 193 nm. Preference is given to fluorine substituted saturated hydrocarbon groups of 10 to 10.

Among the substituents, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable for the same reasons as R ¹ of the general formula (1-1).

Preferred f is 1 or 2. In addition, the position of the substituent is preferably a bridge position.

Preferred examples of the general formula (1-5) include compounds represented by the following formulas.

In Formula 1-6, R ⁸ and R ^{8 '} is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine substituted hydrocarbon group having 1 to 10 carbon atoms, A -Si (R ⁹ ) ₃ group or a -SO ₃ R ¹⁰ group, g and h each represent an integer of 0 to 6, n8 and n9 represent an integer of 1 to 3, and R ⁹ and R ¹⁰ have 1 carbon number To alkyl group of 10.

R ⁸ and R ^{8 '} are the same as R ¹ of Formula 1-1.

Substituents of R ⁸ and R ^{8 ′} in the general formula (1-6) include an aliphatic saturated hydrocarbon group of 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group of 3 to 14 carbon atoms, cyano group, and fluorine in view of excellent radiation transmittance of 193 nm. Preference is given to atoms and fluorine-substituted saturated hydrocarbon groups having 1 to 10 carbon atoms.

Among the substituents, an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable for the same reasons as R ¹ in the general formula (1-1).

Preferred g and h are 0, 1 or 2, n8 and n9 are 1 to 3, particularly preferably 1 or 2.

The specific example of preferable compound 1-6 is shown below.

Preferred examples of the general formula (1-6) include 5-silacyclo [4,4] nonane.

In formula (1-7), R ¹¹ and R ¹² are an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine substituted hydrocarbon group having 1 to 10 carbon atoms,- A Si (R ⁹ ) ₃ group or a -SO ₃ R ¹⁰ group, n10 and n11 each independently represent an integer of 1 to 3, j, k represent an integer of 0 to 6, and R ¹¹ and R ¹² are each When there are a plurality of these, R ¹¹ and R ¹² may be the same or different, two or more R ¹¹ may combine with each other to form a ring structure, or two or more R ¹² may combine with each other to form a ring structure X may represent a single bond, a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, and R ⁹ and R ¹⁰ represent an alkyl group having 1 to 10 carbon atoms.

R ¹¹ and having 1 to 10 aliphatic hydrocarbon group of R ^12, an alicyclic hydrocarbon group having 3 to 14, a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms, -Si (R ⁹⁾ ₃ group, or -SO ₃ R ¹⁰ groups It is the same as the aliphatic hydrocarbon group, alicyclic hydrocarbon group, fluorine-substituted hydrocarbon group, -Si (R ⁹ ) ₃ group, and -SO ₃ R ¹⁰ group in the formula (1-1).

As the substituents of R ¹¹ and R ¹² in the general formula (1-7), an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, a cyano group, and a fluorine atom in view of excellent radiation transmittance of 193 nm And a fluorine-substituted saturated hydrocarbon group having 1 to 10 carbon atoms is preferable.

Moreover, as a C2-C10 divalent aliphatic hydrocarbon group of X, an ethylene group and a propylene group are mentioned, As a C3-C14 bivalent alicyclic hydrocarbon group, a divalent group derived from cyclopentane, cyclohexane, etc. are mentioned. Can be mentioned.

In formula (1-7), X is preferably a single bond. The specific example of preferable compound 1-7 is shown below.

Preferred examples of the general formula (1-7) include dicyclohexyl and dicyclopentyl.

In Formula 1-8, R ¹³ is an alkyl group having 2 or more carbon atoms, an alicyclic hydrocarbon group having 3 or more carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine substituted hydrocarbon group having 2 to 10 carbon atoms, a -Si (R ⁹ ) ₃ group, or- Represents a SO ₃ R ¹⁰ group, p represents an integer of 1 to 6, and when a plurality of R ¹³ are present, these R ¹³ may be the same or different, and two or more R ¹³ may combine with each other to form a ring structure; R ⁹ and R ¹⁰ may be an alkyl group having 1 to 10 carbon atoms.

Preferred R ¹³ is an alkyl group having 2 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, preferred p is 1 or 2, and particularly preferred p is 1.

The alkyl group having 2 or more carbon atoms is preferably an alkyl group having 2 to 10 carbon atoms, and may include a methyl group, an ethyl group, an n-propyl group, and the like. The alicyclic hydrocarbon group having 3 or more carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and includes a cyclohexyl group, a norbornyl group, and the like. A fluorine-substituted hydrocarbon group having 2 to 10 carbon atoms, a -Si (R ⁹ ) ₃ group or a -SO ₃ R ¹⁰ group is a fluorine-substituted hydrocarbon group represented by Formula 1-1, a -Si (R ⁹ ) ₃ group, -SO ₃ R ¹⁰ Same as the group. Examples of the ring structure in which two or more R ¹³ 's are bonded to each other include a cyclopentyl group, a cyclohexyl group, and the like.

The specific example of the preferable compound in General formula (1-8) is shown below.

In Formula 1-9, R ¹⁴ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine substituted hydrocarbon group having 1 to 10 carbon atoms, and -Si (R ⁹⁾ represents ₃ or -SO ₃ R ¹⁰ group, n12 represents an integer of 1 to 3, q is an integer of 0 to 9, R ¹⁴ is, if a plurality is present, these R ¹⁴ are the same or different And R ⁹ and R ¹⁰ represent an alkyl group having 1 to 10 carbon atoms.

R ¹⁴ is the same as R ¹ in Formula 1-1. In addition, preferable R <^14> is the same as that of preferable R <^1> . Preferred q is the same as a.

The specific example of the preferable compound in General formula (1-9) is shown below.

Particularly preferred compounds in the formulas (1-1) to (1-9) have the chemical structures represented by the formulas (1-1) and (1-4), and these compounds are unsubstituted, aliphatic saturated hydrocarbon groups having 1 to 10 carbon atoms, and 3 to 3 carbon atoms. It is a compound substituted with the alicyclic saturated hydrocarbon group of 14, Among these, an unsubstituted compound is especially preferable.

The compound is a liquid at the temperature at which the immersion exposure apparatus operates, and the refractive index is higher than that of pure water, and is preferable for the reasons of Equations iii and iv described above.

Specifically, the refractive index is a value between water and the resist film (or upper layer film for liquid immersion) before exposure, and is preferably higher than water, and the refractive index at 25 ° C. and a wavelength of 193 nm is preferably 1.45 to 1.8. Has a refractive index in the range of 1.6 to 1.8, 25 ° C., and a wavelength of 248 nm of 1.42 to 1.65, preferably 1.5 to 1.65. Moreover, the refractive index in 25 degreeC and D line (wavelength 589 nm) is 1.4 or more, Preferably it is 1.4-2.0, More preferably, it is the range of 1.40-1.65.

In addition, since the change of the refractive index according to the change of the use environment causes the defocus, it is preferable that the present compound is a compound which is hardly affected by the temperature and pressure of the refractive index. In particular, it is assumed that the temperature changes in use due to heat generation due to light absorption of the lens and the resist material, so that the temperature dependency of the refractive index is low. Specifically, the absolute value of the change rate dn / dT according to the temperature T of the refractive index n is preferably 5.0 × 10 ⁻³ (° C. ⁻¹ ), more preferably 7.0 × 10 ⁻⁴ (° C. ⁻¹ ) Within.

In addition, from this viewpoint, it is preferable that the specific heat of this compound is large, specifically, it is preferable that the specific heat value is 0.1 cal / g * degreeC or more, More preferably, it is 0.30 cal / g * degree C or more.

Moreover, it is preferable that the said refractive index is hard to be influenced by chromatic aberration, and, as for the said compound, it is preferable that the wavelength dependence of the refractive index in the vicinity of an exposure wavelength is small.

In addition, other characteristics include a range of high permeability in the far-infrared region, viscosity, solubility of gases such as oxygen and nitrogen, contact angle with the lens, resist (or resist upper layer film), surface tension, flash point, and the like. In addition to being preferred, less chemical interaction with the lens and resist material is required. Hereinafter, these characteristics are demonstrated concretely.

The radiation transmittance at 193 nm is preferably 70% or more, particularly preferably 90% or more, and more preferably 95% or more at 25 ° C. In this case, when the transmittance is less than 70%, heat generation due to heat energy generated by light absorption of the liquid is likely to occur, and defocus and distortion of the optical image due to the change in refractive index due to the temperature increase easily occur. In addition, the amount of light reaching the resist film is reduced by the absorption of the liquid, which causes a significant decrease in the throughput.

The viscosity is preferably at most 0.01 Pa · s, particularly preferably at most 0.005 Pa · s when used in an environment where the viscosity at 20 ° C. is 0.5 Pa · s or less, in particular when the gap between the wafer and the lens material is 1 mm or less. to be. When the viscosity exceeds 0.5 Pa · s, liquid does not easily penetrate the gap between the resist film (or the upper layer film for immersion) and the lens material, or the wafer is mounted as a local immersion method or an exposure method as a liquid supply method of the immersion liquid. In the case of using the step-and-scan method of exposing the wafer to the entire surface by moving one stage, a sufficient scan speed cannot be obtained, leading to a significant drop in throughput and a tendency of temperature rise due to friction. Since this exists, it is easy to be influenced by the optical characteristic change by temperature change. In particular, when the gap between the wafer and the lens material is 1 mm or less, the viscosity is preferably 0.01 Pa · s or less for the former reason, in which case the liquid transmittance is increased by reducing the distance (thickness of the liquid film) of the gap. This is preferable because it can hardly be affected by the absorption of liquid.

In addition, when the viscosity is large, bubbles (nanobubbles and microbubbles) are easily generated in the liquid, which is not suitable because the life of the bubbles becomes long.

In addition, the solubility of the gas in the liquid according to the present invention, solubility represented by the mole fraction of the gas in the liquid when the oxygen and nitrogen at 25 ℃, partial pressure of 1 atm (atm) is preferably 0.5 × 10 ^-4 to 70 X 10 ^-4 , more preferably 2.5 x 10 ^-4 to 50 x 10 ^-4, and when the solubility of these gases is 0.5 x 10 ^-4 or less, since the nanobubbles generated from the resist and the like are hardly lost, By light scattering by this, defects of a resist tend to occur at the time of patterning. Moreover, when it is 70x10 <^-4> or more, since the surrounding gas is absorbed at the time of exposure, it becomes easy to be influenced by the change of the optical characteristic by absorption of gas.

Further, the contact angle between the liquid of the present invention and the resist (or the upper layer film for immersion) is preferably 20 ° to 90 °, more preferably 50 ° to 80 °, and a lens material such as quartz glass or CaF ₂ . The contact angle is preferably 90 ° or less, more preferably 80 ° or less. When the contact angle between the liquid of the present invention and the resist (or immersion upper layer film) before exposure is 20 ° or less, liquid is unlikely to invade with respect to the interval, and when the combination of the local immersion method and the step-and-scan method is used as the exposure method, the liquid It becomes easy to scatter in a film | membrane. On the other hand, when the contact angle of the liquid of this invention and the resist (or immersion upper layer film) before exposure is 90 degrees or more, it will become easy to store a gas in the uneven | corrugated resist (or upper layer film) interface, and it will become easy to produce a bubble. This phenomenon is described in Immersion Lithography Modeling 2003 Year-End Report (International SEMATECH).

In addition, when the contact angle of the liquid of the present invention and the lens material exceeds 90 °, bubbles tend to occur between the lens surface and the liquid.

In addition, especially when used in a step-and-scan exposure apparatus with the same local immersion method as is currently used for immersion exposure of water, the liquid of the present invention has a surface tension because the scattering of the liquid during scanning becomes a problem. This is high. Specifically, the surface tension at 20 ° C. is preferably 5 dyn / cm to 90 dyn / cm, more preferably 20 dyn / cm to 80 dyn / cm.

If the contact angle between the liquid and the resist surface of the present invention is not suitable, the contact angle can be improved by using a suitable immersion upper layer film. Since the liquid of this invention is especially low polarity, a contact angle can be made high by using a high polar upper layer film.

Extraction of resist components such as photoacid generators and basic components by the present liquid not only adversely affects the patterning performance of the resist, deterioration of the profile, etc., but also relates to contamination of the liquid itself, such as optical properties of the liquid. This may cause a change in the lens or erosion of the lens. In addition, this makes it difficult to reuse the liquid or frequently requires purification of the liquid. Therefore, it is preferable that there is little contamination by extraction of a liquid. The elution amount can be evaluated by a method such as HPLC, but more precisely, since the absorbance at 193 nm is very sensitive to the incorporation of components in the resist, it can be evaluated by tracking the latter change. As a request for a specific liquid, the absorbance change (absorbance after immersion-absorbance before immersion) after 180 seconds immersion in the immersion experiment according to the "absorption change at the time of resist contact" in the evaluation method described later is 0.05 or less, preferably. Preferably it is 0.02 or less, More preferably, it is 0.005 or less.

The liquid of the present invention is preferably a compound having a low risk of explosion, ignition and ignition under use environment. Specifically, the flash point is preferably 25 ° C or higher, more preferably 50 ° C or higher, and the flash point is preferably 180 ° C or higher, more preferably 230 ° C or higher. Moreover, it is preferable that the vapor pressure in 25 degreeC is 50 mmHg or less, More preferably, it is 5 mmHg or less.

In addition, it is preferable that the harmfulness to the human body and the environment is low, and in particular, a compound having low acute toxicity and no carcinogenicity, mutagenicity, teratogenicity and reproductive toxicity is preferable for the harmfulness to the human body. Specifically, for example, a liquid having an acceptable concentration of preferably 30 ppm or more, more preferably 70 ppm or more and having a negative Ames test result is preferable. Regarding the hazards to the environment, compounds having no persistence and no ecological accumulation are preferred.

In addition, the liquid of the present invention preferably has a purity of 95.0% by weight or more, particularly preferably 99.0% by weight or more, and more preferably 99.9% by weight or more.

In particular, at an exposure wavelength such as 193 nm, the ratio of a compound containing an olefin having a high absorbance, a compound containing an aromatic ring, a sulfur (sulfide, sulfoxide and sulfone structure), a compound containing a halogen, a carbonyl group and an ether group, etc. It is preferable that it is less than 0.01 weight%, and it is especially preferable that it is less than 0.001 weight%.

In addition, since the liquid containing the compound is used in a semiconductor integrated circuit manufacturing process, it is preferable that the metal or metal salt content is low, specifically, the metal content is 100 ppb or less, preferably 10 ppb or less, more preferably. Is 1.0 ppb or less. If the metal content exceeds 100 ppb, the metal ion or metal component may adversely affect the resist film or the like, or may contaminate the wafer.

Examples of the metal include at least one metal selected from Li, Na, K, Mg, Cu, Ca, Al, Fe, Zn, and Ni. These metals can be measured by atomic absorption method.

Moreover, the oxygen concentration in this liquid is 100 ppm (100 microgram / mL) or less, Preferably it is 10 ppm or less, More preferably, it is 2 ppm or less. In addition, especially at the time of exposure, it is preferably within 1 ppm, more preferably within 10 ppb. When the oxygen concentration exceeds 100 ppm, there is a tendency that a decrease in transmittance due to oxidation reaction or the like due to dissolved oxygen tends to occur. In addition, even when an oxidation reaction or the like does not occur, when oxygen is dissolved, for example, as shown in the examples, due to the absorption of dissolved oxygen and ozone generated when irradiating the oxygen, the liquid depends on the dissolved oxygen concentration. Absorbance decreases. In addition, when the liquid is exposed in the presence of oxygen, the generated ozone oxidizes the liquid, so that the liquid deteriorates faster.

In addition, the present liquid is preferably a liquid that does not have light beneficiation, especially when polarized light exposure is performed, since it causes a decrease in optical contrast. Specifically, it is preferable that the compound constituting the liquid is a compound which does not have optical beneficiation (not optically active), and when the liquid constituent compound is a compound having optical beneficiation (optically active), the same amount of optical It is preferred to contain the isomers (present as racemates) and not have optical activity as a whole of the liquid.

The compounds of the present invention can be obtained as commercially available compounds or can be prepared from raw materials available by various conventional synthetic methods. Hereinafter, the manufacturing method of this compound is given and demonstrated.

For example, the compound represented by the formula (2-1) is contained in dry oil obtained from coal coke, petroleum-based catalytic reforming oil and fluid catalytic cracking oil, naphtha cracking oil of ethylene by-products, and the like. Naphthalene or naphthalene derivatives can be prepared by nuclear hydrogenation by catalytic hydrogenation using a suitable catalyst.

The catalytic reforming oil, flow reforming oil and naphtha cracking oil include not only naphthalene and alkylnaphthalene but also sulfur-containing compounds such as benzene, alkylbenzene, phenanthrene, anthracene, other polycyclic aromatics and derivatives thereof, benzothiophene and derivatives thereof, pyridine And nitrogen-containing compounds such as derivatives thereof, and naphthalene and naphthalene derivatives as raw materials can be obtained by separation and purification from a mixture thereof.

Among the naphthalenes and naphthalene derivatives used for the production of the compound 2-1, those having a low content of sulfur-containing compounds among those mentioned above are preferable. In this case, content of a sulfur containing compound becomes like this. Preferably it is 100 ppm or less, More preferably, it is 50 ppm or less. When the content of the sulfur-containing compound exceeds 100 ppm, not only does the sulfur-containing compound become a catalyst poison during contact hydrogenation and interfere with the progress of the nuclear hydrogenation reaction, but also in the sulfur-containing compound in the compound 2-1 When derived sulfur-containing impurities are mixed and not removed by purification, the transmittance at exposure wavelengths such as the liquid 193 nm of the present invention is reduced.

In particular, in the case of producing cis-decalin or trans-decalin and mixtures thereof in Compound 2-1, it is preferable that the purity of naphthalene as a raw material is high, and the purity of preferred naphthalene is 99.0% or more, particularly preferred naphthalene The purity of is 99.9% or more. In this case, when the content of sulfur compound or the like is high as an impurity, the above-described problems occur, and when other naphthalene derivatives, aromatic compounds and derivatives thereof are included as impurities, hydrocarbon compounds having difficulty in separation of hydrogenated impurities are removed. And the purity of the decalin becomes difficult to control.

As the catalyst for catalytic hydrogenation, sulfides such as cobalt molybdenum, nickel molybdenum, nickel tungsten and the like can be used in addition to noble metal catalysts such as nickel-based, platinum, rhodium, ruthenium, iridium and palladium. Of these, nickel-based catalysts are preferred in view of their catalytic activity and cost.

In addition, it is preferable to use these metal catalysts supported on a suitable carrier, and in this case, the catalyst is highly dispersed on the carrier, which not only increases the reaction rate of hydrogenation, but also prevents degradation of the active site under high temperature and high pressure conditions. Increases resistance to poison.

As the carrier, SiO ₂ , γ-Al ₂ O ₃ , Cr ₂ O ₃ , TiO ₂ , ZrO ₂ , MgO, ThO ₂ , diatomaceous earth, activated carbon and the like can be preferably used.

Moreover, as said method of contact hydrogenation, the gas phase method which does not use a solvent, and the liquid phase method which melt | dissolves and reacts the raw material in a suitable solvent can be used. Among these, the vapor phase method is preferable because of its excellent cost and reaction rate.

In the case of using the gas phase method, nickel and platinum are preferable as the catalyst. The higher the amount of the catalyst used, the higher the reaction rate, but the cost is not preferable. Therefore, in order to complete reaction by accelerating reaction rate, it is preferable to make catalyst amount small and to react on conditions with high temperature and hydrogen pressure. Specifically, it is preferable that the amount of catalyst is 0.01 to 10 parts by weight relative to the raw material naphthalene (naphthalene derivative), the hydrogen pressure is 5 to 15 MPa, and the reaction temperature is about 100 ° C to 400 ° C.

In addition, for example, a method of removing naphthalene from an intermediate tetralin using a nickel or platinum and palladium-based catalyst according to the method described in the patent document (Japanese Patent Laid-Open No. 2003-160515) is carried out under moderate conditions. You can also get

In the above reaction, the reaction conversion rate is preferably 90% or more, more preferably 99% or more.

It is preferable to remove impurities, such as an unreacted raw material and a catalyst, by performing appropriate purification | purification after the said reaction.

As the above purification method, purification methods such as fine distillation, water washing, concentrated sulfuric acid washing, filtration and crystallization and combinations thereof can be used. Of these, precision distillation is preferred because it is effective for the removal of other metals from metals derived from nonvolatile catalysts and the removal of components derived from raw materials. Moreover, in order to remove the metal derived from a catalyst, it is preferable to perform the demetalization process with a catalyst.

Among the compounds, tetrahydrodicyclopentadiene is hydrogenated with dicyclopentadiene (exo, endo mixture) or endo dicyclopentadiene, which are known to be useful as raw material monomers for resins for optical lenses and optical films. The obtained tetrahydrodicyclopentadiene can be obtained by refine | purifying by methods, such as distillation. In addition, when it is desired to obtain the exo isomer selectively from dicyclopentadiene, the dicyclopentadiene isomer mixture is isomerized using a suitable catalyst to selectively obtain the exo body, and the above-described hydrogenation reaction is performed or endo ( exo tetrahydrodicyclopentadiene can be selectively obtained by isomerizing endo (endo and exo mixed) tetrahydrodicyclopentadiene obtained by hydrogenation of endo and exo mixed dicyclopentadiene with a suitable catalyst.

The dicyclopentadiene is generally produced by dimerizing cyclopentadiene contained in a large amount in a so-called C ₅ distillate in a thermal decomposition product of naphtha. The dicyclopentadiene is, for example, 5-isopropenyl-Nord If vor, but contains a component derived from C ₅ hydrocarbon distillate, such as norbornene, as impurities, air being contained in these compounds, after hydrogenation and isomerization Hydrocarbon products derived from these impurities remain, making it difficult to purify the tetrahydrodicyclopentadiene which is the final product. Therefore, it is preferable to use what was purified by the method of refine | purifying previously. The purity in this case is preferably 95% by weight or more, more preferably 97% by weight or more.

In addition, the dicyclopentadiene preferably has a small content of a sulfur-containing component which is a catalyst poison for the hydrogenation reaction, and specifically, a sulfur-containing component present in the dicyclopentadiene is preferably 500 ppb or less. More preferably, it is 50 ppb or less. When the amount of the sulfur-containing component is 500 ppb, the hydrogenation reaction in the subsequent step is likely to be inhibited.

Here, the sulfur-containing component means the total amount of sulfur elements present in the form of inorganic or organic compounds such as free sulfur, elemental sulfur, hydrogen sulfide, mercaptans, disulfides and thiophene, and sulfur chemicals. It can analyze by gas chromatography etc. provided with a luminescence detector (SCD). The said sulfur distillate can be removed by the method of Unexamined-Japanese-Patent No. 2001-181217, for example. Hydrogenation of the said dicyclopentadiene can be performed using a well-known hydrogenation catalyst of a carbon-carbon double bond. The hydrogenation can be performed, for example, by a method disclosed in Japanese Patent Laid-Open No. 60-209536 and Japanese Patent Laid-Open No. 2004-123762. Tetrahydrodicyclopentadiene can be obtained by distillation after the hydrogenation described above. For example, a method of isomerizing using various Lewis acids is known in order to selectively obtain exo bodies. This isomerization can be performed by the method which used aluminum halide, sulfuric acid, etc. as Lewis acid, for example (Japanese Patent Laid-Open No. 2002-255866). In this reaction, it is known that adamantane is produced as a by-product, but when Adamantane is present in a large amount, the transmittance at 193 nm decreases, so that the amount of adamantane coexisting in the final liquid is 0.5% by weight or less. Preferably, it is 0.1 weight%, More preferably, it is necessary to set it as 0.05 weight% or less. The adamantane can be appropriately set under the conditions of the isomerization reaction or removed by various known purification methods.

Hereinafter, the specific example of the structure of a liquid immersion exposure liquid, and a physical property value are shown in following Table 1.

In addition, various physical property data of trans-decalin and exo-tetrahydrodicyclopentadiene are shown in Table 2 below.

In Table 2, the values of oxygen solubility and nitrogen solubility are values when partial pressure is 1 atm, and the unit is ppm.

Since the liquid for liquid immersion exposure of the present invention has a structure selected from Chemical Formulas 1-1 to 1-9, for example, the absorbance at 193 nm is small and preferable, but the absorbance in the wavelength region is easily affected by trace impurities. . In addition, when a base component exists in these liquids, even a very small amount has a big influence on a resist profile. These impurities can be removed by purifying the liquid by a suitable method. For example, for saturated hydrocarbon compounds having the structures of Formulas 1-1 to 1-5 and 1-7 to 1-9, permanganate under concentrated sulfuric acid washing, washing with water, alkali washing, silica gel column purification, fine distillation and alkaline conditions It can be purified by treatment and combinations thereof.

Specifically, for example, the concentrated sulfuric acid washing may be repeated until the colored sulfuric acid is no longer colored, and then the concentrated sulfuric acid is removed by washing with water and alkali, and further purified by distillation after washing and drying. have.

In addition, depending on the compound, impurities can be removed more efficiently by treating with permanganate under alkaline conditions before performing the electric treatment.

During the above purification operation, concentrated sulfuric acid washing is a preferable purification method because it is effective for removing aromatic compounds having a high absorption at 193 nm and compounds having carbon-carbon unsaturated bonds, and is also effective for removing trace basic compounds. The treatment is preferably performed by selecting the optimum stirring method, temperature range, treatment time and treatment frequency depending on the compound to be purified.

Specifically, the higher the temperature, the higher the efficiency of impurity removal, but at the same time, there is a tendency that impurities which cause absorption due to side reactions tend to be easily generated. Preferred treatment temperatures are -20 deg. C to 40 deg. C, and particularly preferred treatment temperatures are -10 deg. C to 20 deg.

As for the treatment time, the reaction between the aromatic compound and the impurity having a carbon-carbon unsaturated bond progresses and the removal efficiency of the impurity increases, but the amount of generation of impurities that cause absorption by side reaction tends to increase. have.

In the case of purification by the concentrated sulfuric acid treatment, the acidic impurities derived from the concentrated sulfuric acid remaining in the liquid of the present invention after the treatment and the sulfonic acid components generated by the concentrated sulfuric acid treatment are completely removed. It is preferable to perform the treatment.

In addition, by performing fine distillation after washing with concentrated sulfuric acid, impurities that cause absorption can be removed more efficiently.

The fine distillation is preferably carried out in a distillation column having a theoretical number of the singular or more than the theoretical number necessary for the separation, depending on the difference between the impurities for removal and the liquid point of the present invention. The theoretical number of stages is preferably 10 to 100 stages from the viewpoint of impurity removal. However, if the theoretical number of stages is increased, the equipment and manufacturing cost increase, so that purification in lower stages is possible by combining with other purification methods. Particularly preferred theoretical stages are 30 to 100 stages.

In addition, it is preferable to perform the said fine distillation on suitable temperature conditions. When the distillation temperature is high, there is a tendency that the reduction effect of absorption is reduced by the oxidation reaction of the compound or the like. Preferred distillation temperatures are 30 ° C. to 120 ° C., particularly preferred distillation temperatures are 30 ° C. to 80 ° C.

In order to perform distillation in said temperature range, it is preferable to perform the said fine distillation under reduced pressure as needed.

It is preferable to perform the said purification process in inert gas atmosphere, such as nitrogen or argon. In this case, it is preferable that the oxygen concentration and organic component concentration in an inert gas are low. Preferred oxygen concentrations are 1000 ppm or less, more preferably 10 ppm or less, particularly preferably 1 ppm or less.

In addition, the treatment with permanganate during the treatment is particularly effective for the removal of non-aromatic carbon-carbon unsaturated bond-containing compounds, but because the oxidation reaction of tertiary carbon tends to occur for compounds having tertiary carbon, tertiary It is preferred for the purification of compounds that do not have carbon.

Moreover, it is preferable to perform the said process at low temperature below room temperature from a viewpoint of preventing a side reaction.

As an example, (cis, trans mixture: Aldrich Co., Ltd.) decalin, trans-decalin (Togase Kasei Co., Ltd.), refine | purified by the method shown in Example 1 mentioned later, and after purification, trans-decalin (1) After purification by dicyclohexyl, isopropylcyclohexane, cyclooctane, cycloheptane, and the method shown in Example 2, after purification by the method shown in trans-decalin (2) and Example 3, after purification exo After purification by the method shown in -tetrahydrodicyclopentadiene (1) and Example 4, after purification by the method shown in exo-tetrahydrodicyclopentadiene (2) and Example 5, after purification trans After purification by the method shown in decalin (3) and Example 6, after purification by the method shown in exo-tetrahydrodicyclopentadiene (3) and Example 7, after purification, dicyclohexyl and iso Propylcyclohexane, simultaneously The measurement results of the refractive index and transmittance of chlorooctane and copper cycloheptane are shown in Tables 3 and 4 below. In addition, acetonitrile as a reference liquid, pure water used as a liquid for immersion exposure, and methylene iodide were used as comparative examples.

The refractive index was measured in the ultraviolet region for cis, trans-decalin and after purification for trans-decalin, dicyclohexyl, isopropylcyclohexane, cyclooctane, cycloheptane and acetonitrile. The measuring apparatus used UV-VIS-IR which is a form of the goniometer-spectrometer made from MOLLER-WEDEL, and the measuring method was measured at the measurement temperature of 25 degreeC by the minimum polarization method.

The transmittance was performed by measuring method A or measuring method B. Measurement method A performs liquid sampling on the cell of 10 mm of optical path lengths with a cover made of polytetrafluoroethylene in the glove box of nitrogen atmosphere which kept oxygen concentration below 0.5 ppm, and is made by Nippon Bunko company JASCO-V-550 Was measured using air as the reference. The value in a table | surface is the value converted into the optical path length of 1 mm based on this value after correct | amending the cell reflection by calculation.

Measuring method B is a liquid crystal in a quartz cell equipped with a polytetrafluoroethylene cover (for measurement: optical path length of 50 mm, reference: optical path length of 10 mm) in a glove box of nitrogen atmosphere with an oxygen concentration of 0.5 ppm or less. Sampling was performed. Using the above-mentioned cell, Nippon Bunko Co., Ltd. JASCO-V-550 measured the 50-mm optical path length cell based on the cell of 10-mm optical path length which is a sample. The value of this measurement was made into the absorbance per 40 mm of optical path lengths. The value in a table | surface is converted into the value per 1 mm of optical path lengths based on this value.

As shown in Tables 3 and 4, the wavelength dependence of the refractive index increases as the wavelength decreases, and the liquid of the present invention in the above table has a high refractive index of 1.58 or more at 193 nm, for example.

In addition, since the compound of the present invention is a low polar compound, the solubility of gases such as oxygen and nitrogen is high. For this reason, it is easy to be influenced by the dissolution of these gases, for example, when it is left in an atmospheric atmosphere, absorption of dissolved oxygen or absorption of ozone generated by excitation of dissolved oxygen by light, or oxidation reaction involving dissolved oxygen. For example, there exists a tendency which the fall of the transmittance | permeability of 193 nm arises, for example. For this reason, these compounds are preferably degassed and stored in an inert gas such as nitrogen and argon with little absorption. Specifically, the oxygen concentration in the storage liquid is preferably 100 ppm or less, more preferably 10 ppm or less. In addition, when deoxygenation cannot be carried out before exposure, 1 ppm or less is especially preferable, More preferably, it is 10 ppb or less.

Hereinafter, the liquid immersion exposure method using the liquid immersion exposure liquid of this invention is demonstrated.

The liquid for liquid immersion exposure of the present invention is preferably stored in an inert gas as described above, but as the container at this time, in a container without elution of a container component or a component of the container lid (for example, a plasticizer compounded in plastic) It is desirable to preserve. Examples of preferred containers include, for example, glass, metal (eg, SUS), pottery, PTFE (polytetrafluoroethylene), PFEP (perfluoroethylenepropene copolymer), and ECTFE (ethylene-chlorotrifluoro). Ethylene copolymer), PTFE / PDD (polytetrafluoroethylene-perfluorodioxol copolymer), PFA (perfluoroalkoxyalkane), ETFE (ethylene-tetrafluoroethylene copolymer), PVDF (polyvinylidene fluorine) The container which is a fluorine resin, such as a lide), PVE (polyvinyl fluoride), and PCTFE (polychlorotrifluoroethylene), is mentioned, Especially preferably, it is a container whose material is glass and a fluororesin.

In addition, examples of the lid of the preferred container include, for example, a lid made of polyethylene and not containing a plasticizer, or made of glass, metal (eg, SUS), ceramics, PTFE (polytetrafluoroethylene), or PFEP (perfluoro). Low ethylene propene copolymer), ECTFE (ethylene-chlorotrifluoroethylene copolymer), PTFE / PDD (polytetrafluoroethylene-perfluoro dioxol copolymer), PFA (perfluoroalkoxyalkane), ETFE (Ethylene-tetrafluoroethylene copolymer), a cover which is fluororesins, such as PVDF (polyvinylidene fluoride, PVF (polyvinyl fluoride), and PCTFE (polychlorotrifluoroethylene), is mentioned.

Moreover, about the piping used when sending liquid from a container to an exposure machine, it is preferable that it is the piping which does not produce the same elution as mentioned above, As a material of a preferable piping, glass, metal, pottery, etc. are mentioned.

When the liquid for immersion exposure of the present invention is used for immersion exposure, the fine particles and bubbles (microbubbles) cause defects in the pattern, etc., and therefore, it is preferable to remove the dissolved gas that causes the particles and bubbles before exposure.

As a method of removing fine particles, a method of filtration using an appropriate filter may be mentioned.

As a filter, the removal efficiency of microparticles | fine-particles is favorable, and the filter using the material which does not change the absorption in the exposure wavelength by elution at the time of filtration is preferable. Preferred filter materials include, for example, glass, metals (e.g., SUS and silver) and metal oxides, PTFE (polytetrafluoroethylene), PFEP (perfluoroethylenepropene copolymer), ECTFE (ethylene-chloro Trifluoroethylene copolymer), PTFE / PDD (polytetrafluoroethylene-perfluorodioxol copolymer), PFA (perfluoroalkoxyalkane), ETFE (ethylene-tetrafluoroethylene copolymer), PVDF (poly Fluorine resins such as vinylidene fluoride), PVF (polyvinyl fluoride) and PCTFE (polychlorotrifluoroethylene). Moreover, it is preferable that it is a material chosen from the preferable material of said filter also about the material of peripheral parts, such as a housing, a core, a support, and a plug of a filter.

Examples of the method for removing the dissolved gas include a reduced pressure degassing method, an ultrasonic degassing method, a degassing method using a gas permeable membrane, and a degassing method using various degassing apparatuses.

Since the liquid for liquid immersion exposure of the present invention becomes part of the optical system at the time of exposure, it is preferable to use it in an environment where there is no influence of optical property changes such as refractive index of the liquid. For example, it is preferable to use it in the environment which made the temperature, pressure, etc. which affect the optical characteristic of a liquid constant. For example, the temperature is preferably kept in the range of ± 0.1 ° C, more preferably ± 0.01 ° C.

The liquid immersion exposure using the liquid of the present invention can also be performed in an atmospheric atmosphere. However, as described above, the solubility of oxygen in the liquid of the present invention is high and the absorption characteristics at the exposure wavelength may be affected. It is preferable to expose in an inert gas which has little absorption at the exposure wavelength and does not cause a chemical reaction with the liquid. As said preferable inert gas, nitrogen, argon, etc. are mentioned, for example.

Moreover, it is preferable to keep the concentration of the organic component in a use atmosphere below a certain level from the viewpoint of preventing the absorption characteristic change in the exposure wavelength of the liquid due to contamination by the organic component in the air. As a method of maintaining this organic component concentration, not only the thing of high purity in the said inert gas atmosphere, but the method of using the filter and various gas refinery tubes (apparatus) which adsorb | suck an organic component, etc. are mentioned. In order to maintain the concentration, it is desirable to perform the analysis of the ambient atmosphere on a regular basis. For this purpose, various assays using, for example, gas chromatography can be used.

As a liquid supplying method of the liquid immersion in the exposure area, a moving pool method, a seaming stage method, and a local fill method (local immersion method) are known (document [special seminar immersion exposure technology]). (See May 27, 2004) Seminar text)), the local immersion method is preferable because the amount of the liquid for immersion exposure is at least irrelevant.

As a final (objective) lens material for liquid immersion exposure using this liquid, current CaF ₂ or fused silica is preferable from its optical characteristics. As other preferable lens materials, for example, fluorine salts of high cycle alkaline earth metal M and salts represented by the formulas Ca _x M _{1 - x} F ₂ , oxides of alkaline earth metals such as CaO, SrO and BaO, and the like are preferable. When the material is used, since the refractive index of the lens is higher than that of CaF ₂ (n @ 193 nm = 1.50) and fused silica (n @ 193 nm = 1.56), especially a high NA lens having a numerical aperture greater than 1.5 is designed and It is preferable when processing.

The liquid of the present invention can be reused after use because the extraction of the resist component is very small. In the case of using a resist (or resist upper layer film) which can ignore the effects of elution from the resist film during exposure, the liquid of the present invention can be reused without being purified, but in this case, after treatment such as degassing and filtration, It is preferable to reuse. It is preferable to perform these processes inline from a viewpoint of simplifying a process.

In addition, even if the use of the above-described elution from the resist film and the like are negligible at one time, when the number of times of use exceeds a certain number of times, the physical properties of the liquid are expected to change due to the influence of accumulated impurities. It is preferable to recover and purify after use a certain number of times.

Examples of the purification method include washing with water, acid washing, alkali washing, fine distillation, purification using a suitable filter (filling column), filtration and the like, and the above-mentioned liquid purification method or a combination of these purification methods. Can be mentioned. Among these, it is preferable to perform purification by washing with water, alkali washing, acid washing, fine distillation or a combination of these purification methods.

The alkali cleaning is the removal of acid generated by exposure eluted to the liquid of the present invention, the acid cleaning is the removal of the basic component in the resist eluted to the liquid of the present invention, and the water washing treatment is performed to remove the acid in the resist film eluted to the liquid of the present invention. It is effective for the removal of eluates such as generators, basic additives and acids generated during exposure.

The fine distillation is effective not only for the removal of low volatile compounds in the additive but also for removing hydrophobic components generated by decomposition of the protecting group in the resist during exposure.

The liquids for liquid immersion exposure represented by the formulas (1-1) to (1-9) may be used alone or as mixtures, respectively. As a preferable example, it is the case of using independently. By using it alone, it becomes easy to set liquid immersion exposure conditions.

In addition, the liquid of the present invention can be mixed with liquids other than the present invention as needed, and thereby, for example, optical property values such as refractive index and transmittance, and physical property values such as contact angle, specific heat, viscosity, and expansion coefficient to desired values. can do.

As a liquid other than the present invention used for this purpose, not only the other immersion-exposed solvents, but also various antifoaming agents, surfactants, etc. can be used, and it is effective in reducing a bubble or adjusting surface tension.

The liquid immersion exposure is performed using the liquid immersion exposure liquid.

A photoresist film is formed by applying a photoresist on the substrate. As the substrate, for example, a silicon wafer, a wafer coated with aluminum, or the like can be used. In addition, since the potential of the resist film is taken out to the maximum, for example, as disclosed in Japanese Patent Application Laid-Open No. Hei 6-12452 or the like, an organic or inorganic antireflection film can be formed on a substrate to be used.

The photoresist used is not specifically limited, It can select suitably according to the purpose of use of a resist. As a resin component of a photoresist, the polymer containing an acid dissociable group is mentioned. It is preferable that the acid dissociable group is not decomposed by exposure, and in particular, it is preferable that the product after the decomposition is volatilized under exposure conditions, so that it does not elute to the liquid of the present invention. Examples of these polymers include resins containing alicyclic groups, lactone groups, derivatives thereof, and the like, resins containing hydroxystyrene derivatives and the like in the polymer side chain.

In particular, a photoresist using a resin containing an alicyclic group, a lactone group and derivatives thereof in the polymer side chain is preferable. Since these photoresists contain a chemical structure similar to a cyclic hydrocarbon compound containing an alicyclic hydrocarbon compound or a silicon atom in a ring structure, the photoresist is excellent in affinity with the liquid for immersion exposure of the present invention. Further, the photoresist film is not eluted or dissolved.

Examples of the photoresist include a chemically amplified positive or negative type resist containing additives such as a polymer containing an acid dissociable group, an acid generator, and an acid diffusion control agent as the resin component.

When using the liquid for liquid immersion exposure of this invention, especially a positive resist is preferable. In the chemically amplified positive resist, the acid dissociable organic group in the polymer is dissociated by the action of the acid generated from the acid generator upon exposure to generate, for example, a carboxyl group. As a result, the solubility of the resist in the alkaline developer of the exposed portion. This becomes high, and this exposure part is melt | dissolved and removed by alkaline developing solution, and a positive resist pattern is obtained.

The photoresist film is prepared by dissolving a resin composition for forming a photoresist film in a suitable solvent, for example, at a solid content concentration of 0.1 to 20% by weight, and then filtering, for example, with a filter having a pore size of about 30 nm. The resist solution is formed by applying onto the substrate by a suitable coating method such as spin coating, cast coating and roll coating, followed by preliminary firing (hereinafter referred to as "PB") to volatilize the solvent. In this case, a commercially available resist solution can be used as it is. It is preferable that the photoresist film has a higher refractive index than the liquid immersion upper layer film and the liquid immersion exposure liquid, and specifically, the refractive index n _RES of the photoresist film is preferably in the range of 1.65 or more. In particular, when NA is 1.3 or more, n _RES is preferably larger than 1.75. In this case, a decrease in contrast of exposure light due to an increase in NA can be prevented.

In the liquid immersion exposure method, a liquid immersion upper layer film can be further formed on the photoresist film.

As the upper layer film for liquid immersion, a protective film can be formed on the photoresist film without sufficient permeability to the wavelength of the exposure light and without intermixing with the photoresist film, and maintains a stable film without being eluted to the liquid used during the liquid immersion exposure. It can be used if it is a film which can be peeled off before development. In this case, it is preferable that the upper layer film is peeled off at the time of development as long as it is a film that is easily dissolved in an alkaline solution that is a developer.

As a substituent for giving alkali solubility, it is preferable that it is resin which has at least 1 group of a hexafluoro carbinol group and a carboxyl group in a side chain.

It is preferable that the immersion upper layer film has a multiple interference prevention function at the same time, and in this case, it is preferable that the refractive index n _OC of the immersion upper layer film is a formula shown below.

n _OC = (n _lq × n _RES ) ^0.5

Here, n _lq represents the refractive index of the liquid for immersion exposure, and n _RES represents the refractive index of the resist film, respectively.

Specifically, n _OC is preferably in the range of 1.6 to 1.9.

The liquid immersion upper layer film is dissolved and dissolved in a solvent which is not intermixed with the resist film on the resist film at a solid content concentration of 0.01 to 10%, and then applied and prebaked by the same method as in the formation of the photoresist film. It can form by doing.

The resist pattern is formed by irradiating a photoresist film or a photoresist film on which the immersion upper layer film is formed by irradiating the radiation of the liquid immersion exposure liquid of the present invention through a mask having a predetermined pattern as a medium, and then developing. This step is a step of developing after performing liquid immersion exposure, firing at a predetermined temperature.

The radiation used for the immersion exposure is, for example, visible light depending on the photoresist film and the combination of the photoresist film and the immersion upper layer film; ultraviolet rays such as g-ray and i-ray; Far ultraviolet rays such as excimer laser; X-rays, such as synchrotron radiation; Various radiations, such as charged particle beams, such as an electron beam, can be selected and used. In particular, ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm) is preferable.

Moreover, in order to improve the resolution, pattern shape, developability, etc. of a resist film, it is preferable to perform post-exposure baking (henceforth "PEB"). Although this baking temperature is suitably adjusted with the resist etc. used, it is about 30-200 degreeC normally, Preferably it is 50-150 degreeC.

Subsequently, the photoresist film is developed with a developer and washed to form a desired resist pattern.

In order to evaluate the liquid for liquid immersion exposure, the resist film was formed using the radiation sensitive resin composition shown below. Moreover, the upper layer film for liquid immersion shown below was formed in one part. This evaluation resist film was used to measure properties (elution test, film solubility test and patterning evaluation) as a liquid for immersion exposure.

Reference Example 1

Resin used for a radiation sensitive resin composition was obtained by the following method.

Dissolve 39.85 g (40 mol%) of compound (S1-1), 27.47 g (20 mol%) of compound (S1-2), and 32.68 g (40 mol%) of compound (S1-3) in 200 g of 2-butanone Then, a monomer solution containing 4.13 g of methyl azobisiso valerate was prepared, and a 1000 ml three-necked flask containing 100 g of 2-butanone was purged with nitrogen for 30 minutes. After nitrogen purging, the reaction vessel was heated to 80 ° C while stirring, and the monomer solution prepared in advance was added dropwise over 3 hours using a dropping funnel. The dropping start was taken as the polymerization start time, and the polymerization reaction was carried out for 5 hours. After completion of the polymerization, the polymerization solution is cooled to 30 ° C. or lower by water cooling, poured into 2000 g of methanol, and the precipitated white powder is separated by filtration. The filtered fractionated white powder was washed on a slurry with 2 degrees 400 g of methanol, then filtered fractionated and dried at 50 ° C. for 17 hours to give a polymer of white powder (75 g, yield 75% by weight). This polymer has a molecular weight of 10,300 and has a repeating unit represented by the compound (S1-1), the compound (S1-2) and the compound (S1-3) as a result of ¹³ C-NMR analysis, and the content of each repeating unit is 42.3: It was a copolymer of 20.3: 37.4 (mol%). This polymer is referred to as resin (A-1).

Reference Example 2

Resin used for a radiation sensitive resin composition was obtained by the following method.

53.92 g (50 mol%) of compound (S2-1), 10.69 g (10 mol%) of compound (S2-2), and 35.38 g (40 mol%) of compound (S2-3) were dissolved in 187 g of 2-butanone. A solution (2) in which 3.37 g of a monomer solution (1) and 3.37 g of dimethyl 2,2'-azobis (2-methylpropionate) was dissolved in 64 g of 2-butanone was prepared, and 15 g of 2-butanone was added thereto. Into a 1000 ml three-necked flask, 28.77 g of the monomer solution (1) prepared above and 4.23 g of the solution (2) were added, followed by purging with nitrogen under reduced pressure. After purging with nitrogen, the reaction vessel was heated to 80 ° C while stirring, and after 15 minutes, 258.98 g of monomer solution (1) and 24.64 g of solution (2) were added dropwise over 3 hours using a liquid feeding pump. After completion of the dropwise addition, the mixture was stirred for a further 4 hours. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C. or lower by cooling. After completion of the reaction, the solution was left to cool and cooled to 30 ° C. or lower, and then poured into 4000 g of isopropyl alcohol to separate the precipitated white powder by filtration. The filtered fractionated white powder was washed on a slurry with 2 degrees 2000 g of isopropyl alcohol, then filtered off and dried at 60 ° C. for 17 hours to give a polymer of white powder (85 g, yield 85% by weight). This polymer has a Mw of 7,600 and a repeating unit represented by the compound (S2-1), the compound (S2-2) and the compound (S2-3) as a result of ¹³ C-NMR analysis, and the content of each repeating unit is 53.1: It was a copolymer which is 8.5: 38.4 (mol%). This polymer is referred to as resin (A-2).

Reference Example 3

Resin which forms the upper layer film for liquid immersion was obtained by the following method.

50 g of compound (S3-1), 5 g of compound (S3-2), 25 g of compound (S3-3), 20 g of compound (S3-4), and 6.00 g of methyl azobisiso valerate 200 g of methyl ethyl ketone It melt | dissolved in and prepared the monomer solution which made it into a uniform solution. Then, a 1000 ml three-necked flask containing 100 g of methyl ethyl ketone was purged with nitrogen for 30 minutes. After purging with nitrogen, the flask was heated to 80 ° C. while stirring, and the above-prepared monomer solution was added dropwise at a rate of 10 ml / 5 minutes using a dropping funnel. The polymerization was carried out for 5 hours with the start of dropping being the starting point of the polymerization. After the completion of the polymerization, the reaction solution was cooled to 30 ° C. or lower, and then the reaction solution was poured into 2000 g of heptane, and the precipitated white powder was separated by filtration. The filtrate-separated white powder was mixed with 400 g of heptane, and the operation of stirring as a slurry was washed twice. The filtrate was separated by filtration and dried at 50 ° C. for 17 hours to obtain a white powder of resin (E-1). (89 g, yield 89% by weight). Resin (E-1) had a Mw of 7,300.

Reference Example 4

Resin which forms the upper layer film for liquid immersion was obtained by the following method.

As the monomer, except that 70 g of compound (S4-1), 20 g of compound (S4-2) and 10 g of compound (S4-3) were used, the white powder of resin (E-2) was obtained in the same manner as in Reference Example 3. It was obtained (88 g, yield 88% by weight). Resin (E-2) had a Mw of 6,800.

Reference Example 5

The radiation sensitive resin composition was obtained by the following method.

The radiation-sensitive resin compositions (F1 to F3) were prepared by mixing the resins, acid generators, acid diffusion control agents and solvents shown in Table 5 below to form a uniform solution, followed by filtration with a membrane filter having a pore size of 200 nm. Parts in Table 5 are by weight.

In addition, the acid generator (B), acid diffusion control agent (C), and solvent (D) used are shown below.

Acid Generator (B)

B-1: 4-nonafluoro-n-butylsulfonyloxyphenyl diphenylsulfonium nonafluoro-n-butanesulfonate,

B-2: triphenylsulfonium nonafluoro-n-butanesulfonate

Acid Diffusion Controls (C)

C-1: 2-phenylbenzimidazole

Solvent (D)

D-1: Propylene Glycol Monomethyl Ether Acetate

Reference Example 6

The upper layer film composition for liquid immersion was obtained by the following method.

After mixing the resin and solvent shown in Table 6 to make a uniform solution, the upper layer film composition (G1 and G2) for liquid immersion was manufactured by filtering by the membrane filter of 200 nm of pore diameters. In Table 6 below, n-BuOH represents normal butanol and parts are by weight.

Reference Example 7

Evaluation resist films (H-1 to H-5) were obtained by the following method.

After coating the lower layer anti-reflection film ACR29 (manufactured by Brewer Science Co., Ltd.) by spin coating and PB (90 ° C, 60 seconds) on an 8-inch silicon wafer to form a coating film having a film thickness of 77 nm, the following table was used under the same conditions. The resist film (film thickness 205 nm) was formed using the radiation sensitive resin composition shown in 7 (H-1 to H-3).

In addition, after forming a resist film (film thickness 205 nm) using a radiation sensitive resin composition by the method similar to the above, spin coating, PB (130 degreeC, 90 second) to form an upper layer film having a thickness of 32 nm (H-4 and H-5).

Example 1

Commercially available trans-decalin (trans-decahydronaphthalene) was purified by the following method to obtain a liquid for liquid immersion exposure.

100 ml of commercially available trans-decalin (manufactured by Tokyo Chemical Industries, Ltd .; 193 nm in terms of optical path length of 1 mm is 10% or less) was charged into a 200 ml flask equipped with a glass-coated stirrer chip, and 20 ml of concentrated sulfuric acid ( Wako Pure Chemical Industries, Ltd.) was set, and the rotation speed of the stirrer chip was set to 500 to 1000 rpm, and stirred at 25 ° C. for 20 minutes. Thereafter, concentrated sulfuric acid was removed by liquid separation, and the above operation was performed three times. Thereafter, the separated organic layer was washed once with 50 ml of deionized water and three times with saturated aqueous sodium hydrogen carbonate solution. Thereafter, the organic layer was washed three times with pure water. It was confirmed that pH at this time point was 7 (neutral). Thereafter, the mixture was dried over magnesium sulfate, and after drying, the magnesium sulfate was removed by decantation, and distillation under reduced pressure was carried out with a distillation apparatus equipped with a Weedma rectifier having a pressure of 10 mmHg and a length of 20 cm. Dogs were recovered. The absorbance at 193 nm of each fraction was measured (the measurement conditions were in accordance with the conditions of Measurement Method A in the above paragraph), and there were 12 distillates having an optical path length of 1 mm and a transmittance of 93% or more. A trans-decalin having an optical path length of 1 mm equivalent transmittance of 90% or more was obtained. In addition, each fraction was nitrogen-saturated, and it preserve | saved in the glass container which carried out the nitrogen substitution by degassing under reduced pressure. When the purity of the compound immediately after the container was analyzed by gas chromatography, the purity (hereinafter referred to as "GC purity") was 99.92%. The trans-decalin after purification obtained by the method of Example 1 is called trans-decalin (1) after purification.

In addition, commercially available trans, cis-mixed decalin and commercial cis-decalin were purified by the method described above.

Example 2

Sulfuric acid treatment was carried out in the same manner as in Example 1 under a nitrogen atmosphere. Thereafter, a commercially available trans-decalin (manufactured by Toh Kasei Co., Ltd .; transmittance of 193 nm in terms of optical path length of 1 mm is 10% or less) was purified by the same method as in Example 1, and the transmittance was calculated in terms of optical path length of 1 mm. A 96.8% liquid was obtained. The dissolved oxygen and dissolved nitrogen concentrations of this liquid were analyzed by gas chromatography (detector TCD). The dissolved oxygen concentration was less than 1 ppm (below the detection limit) and the dissolved nitrogen concentration was 119 ppm. In addition, the metal content of Li, Na, K, Mg, Cu, Ca, Al, Fe, Mn, Sn, Zn, and Ni of the present liquid was measured by atomic absorption method. As a result, Ca was 1 ppb, and Zn was 6 ppb. , The other metal was less than 1 ppb (below the detection limit). The trans-decalin after purification obtained by the method of Example 2 is called trans-decalin (2) after purification.

Since this liquid has little metal powder, it can be used not only as a liquid for liquid immersion exposure but also as an optical device used in the visible light region.

In addition, after the purification obtained in Example 2, trans-decalin (2) was left in air to bring air saturation, and the transmittance at 193 nm was measured. The results are shown in Table 8 below.

As shown in Table 8, it was confirmed that the transmittance was increased when the oxygen concentration was not saturated.

In addition, the change of the transmittance | permeability by contact with a resist film was measured by the following method.

In a nitrogen glove box in which nitrogen was substituted and the oxygen concentration was 10 ppm or less, the liquid was dropped for 3 minutes so that the thickness of the liquid film was 0.8 mm on the silicon wafer on which the resist films H-1 and H-4 were formed, and the transmittance at 193 nm. The change of was measured. Pure water was used as a comparative example. The results are shown in Table 9 below.

As shown in Table 9, even after contact with the resist film, the transmittance of the trans-decalin (2) after purification was hardly changed.

After purification, the solubility of the acid generator in trans-decalin (2) was measured by the following method. Triphenylsulfonium nonafluoro-n-butanesulfonate was used as an acid generator, and after purification, a predetermined amount of an acid generator was added to 100 ml of trans-decalin, stirred for 1 hour, and dissolved completely. Solubility was examined by visually confirming whether or not. Pure water was used as a comparative example. The results are shown in Table 10 below.

As shown in Table 10, almost no acid generator was dissolved in trans-decalin (2) after purification.

Example 3

Commercially available exo-tetrahydrodicyclopentadiene was purified by the following method to obtain a liquid for liquid immersion exposure.

100 ml of commercially available exo-tetrahydrodicyclopentadiene (manufactured by Tokyo Chemical Co., Ltd., 193 nm in terms of optical path length of 1 mm is 10% or less) was charged into a 200 ml flask equipped with a glass-coated stirrer chip, After cooling internal temperature to 5 degreeC in the ice-water bath, 20 ml of concentrated sulfuric acid (made by Wako Pure Chemical Industries, Ltd.) was put, and the rotation speed of the stirrer chip was set to 500-1000 rpm, and it stirred at 25 degreeC for 20 minutes. Thereafter, concentrated sulfuric acid was removed by liquid separation, and the above operation was performed three times. Thereafter, the separated organic layer was washed once with 50 ml of deionized water and three times with saturated aqueous sodium hydrogen carbonate solution. Thereafter, the organic layer was washed three times with pure water. It was confirmed that pH at this time point was 7 (neutral). Thereafter, the organic layer was dried using magnesium sulfate, and magnesium sulfate was removed by decantation. The liquid of 91 ml obtained at this point was bubbled with nitrogen for 30 minutes, and the transmittance at 193 nm was measured (measurement conditions were in accordance with the conditions of the above paragraph), which was 87.7% in terms of 1 mm of optical path length. In addition, this liquid was preserve | saved in the nitrogen-substituted glass container after nitrogen-saturated and degassed. The GC purity of the compound immediately after container encapsulation was 99.94%. The exo-tetrahydrodicyclopentadiene after the purification obtained by the method of Example 3 is called exo-tetrahydrodicyclopentadiene (1) after purification.

Example 4

Sulfuric acid treatment was carried out in the same manner as in Example 1 under a nitrogen atmosphere. Thereafter, commercially available exo-tetrahydrodicyclopentadiene was purified by the same method as in Example 3 and distilled under reduced pressure under a nitrogen atmosphere in the same manner as in Example 2, whereby the transmittance was 97.5% in terms of 1 mm of optical path length. A liquid was obtained. The dissolved oxygen and dissolved nitrogen concentrations of this liquid were analyzed by gas chromatography (detector TCD), and the dissolved oxygen concentration was less than 1 ppm (below the detection limit) and the dissolved nitrogen concentration was 100 ppm. The exo-tetrahydrodicyclopentadiene after purification obtained by the method of Example 4 is called exo-tetrahydrodicyclopentadiene (2) after purification.

Example 5

Example 1 was carried out using the nitrogen refine | purified by the nitrogen purifier, except that the whole operation was performed in the glove box which kept nitrogen concentration within 0.5 ppm, and the reduced-pressure distillation was controlled by controlling a decompression degree so that a vapor temperature might be 50 degrees C or less. Commercially available trans-decalin (manufactured by Tokyo Kasei) was carried out in the same manner as described above. It was T = 99.5% when the transmittance | permeability per 1 mm of the compound after refinement was computed based on the value of the absorbance measured by the said measuring method B. When the oxygen concentration at this time was measured by GC (detector TCD), the oxygen concentration was less than 1 ppm and the nitrogen concentration was 119 ppm. In addition, GC purity was 99.92%. The trans-decalin after purification obtained by the method of Example 5 is called trans-decalin (3) after purification.

Example 6

Example 3 was carried out using the nitrogen refine | purified by the nitrogen purifier, except that the whole operation was performed in the glove box which kept nitrogen concentration within 0.5 ppm, and pressure-reduced distillation was adjusted by adjusting the pressure reduction degree so that steam temperature may be 50 degrees C or less. The commercially available exo-tetrahydrodicyclopentadiene (manufactured by Tosug Kasei) was purified in the same manner as in the above. It was T = 99.6% when the transmittance per mm of the compound after purification was calculated based on the value of the absorbance measured by the said measuring method B. The oxygen concentration at this time was measured by GC (detector TCD), and the oxygen concentration was less than 1 ppm and the nitrogen concentration was 100 ppm. In addition, GC purity was 97.80%. The exo-tetrahydrodicyclopentadiene after purification obtained by the method of Example 6 is called exo-tetrahydrodicyclopentadiene (3) after purification.

Example 7

By carrying out sulfuric acid treatment in the same manner as in Example 3, commercially available dicyclohexyl, isopropylcyclohexane, cyclooctane and cycloheptane were purified to obtain a liquid for liquid immersion exposure.

In this embodiment, GC purity analysis is subject to the following conditions.

It was measured by Agilent Technologies' GC6850 (Column Agilent Technologies HP-1 (non-polarized) detector FID). The measurement was performed at the inlet temperature of 250 ° C., the column temperature of 70 ° C. to 300 ° C. (heating method), and the carrier gas under the condition of helium. Purity was calculated | required from area ratio as 100% of the total peak areas of FID.

Examples 8 to 22 and Comparative Examples 1 to 2

Using the above-mentioned evaluation resist film, the liquid immersion exposure liquid of the present invention was subjected to elution test, film solubility test, patterning evaluation (immersion patterning evaluation, immersion exposure evaluation by a two-beam interference exposure machine), and absorbance change (or contamination) upon contact with resist. Evaluated by. The results are shown in Tables 11 to 14 below. In addition, the wavelength dependence of refractive index has a correlation which becomes a high refractive index value as wavelength becomes short, as shown in Table 3. For this reason, it is possible to predict the refractive index in a short wavelength by measuring the refractive index in D line (wavelength 589 nm). In particular, since the liquid for liquid immersion exposure of the present invention has a chemically similar structure to the decalin shown in Table 1, it can be predicted from the refractive index at D line (wavelength 589 nm). Therefore, the refractive index in D line (wavelength 589 nm) was shown. All showed higher values than the refractive index of pure water.

In addition, the liquid for immersion exposure shown in Examples 8-13 was refine | purified according to Example 1, and the liquid for immersion exposure shown in Examples 14-22 is refine | purified according to the method of Example 1.

(1) dissolution test

After the wafer coated with the above-mentioned evaluation resist film was immersed in 300 ml of liquid immersion exposure liquid shown in Table 11 for 30 seconds, the wafer was taken out to check for the presence of impurities in the remaining liquid immersion exposure liquid by HPLC (Shimazu Seisakusho Co., Ltd. column). Inertsil ODS-3 (inner diameter 10 mm x length 250 mm), developing solvent: acetonitrile / water = 80/20, detector: UV @ 205 nm, 220 nm, 254 nm, sample injection amount 4 μm It was measured by. At this time, the dissolution test result x and the case where the impurity more than a detection limit were not confirmed when the impurity more than a detection limit was confirmed by either detector were set as the dissolution test result (circle).

(2) solubility test of membrane

After measuring the initial film thickness of the wafer which apply | coated the said evaluation resist film, it immersed for 30 second in the liquid immersion exposure liquid shown in 300 ml of Table 11, and measured the film thickness again. At this time, it was determined that the liquid immersion exposure liquid did not dissolve the resist film if the amount of decrease in the film thickness was within 0.5% of the initial film thickness. .

(3) patterning evaluation test

Patterning Assessment Exam (1)

The wafer coated with the above-mentioned evaluation resist film was exposed under an optical condition of NA: 0.78, Sigma: 0.85, and 2/3 Ann in an ArF projection exposure apparatus S306C (manufactured by Nikon Corporation) (exposure amount 30 mJ / cm 2) Then, PEB (130 ° C, 90 seconds) was performed with a CLEAN TRACT ART 8 hot plate, and a puddle development (developing component, 2.38 wt% tetra) was performed with the LD nozzle of the clean track Act 8. Hydroammonium hydroxide aqueous solution) (for 60 seconds) and rinsed with ultrapure water, followed by spin drying by rotational vibration for 15 seconds at 4000 rpm (substrate A after development). Subsequently, after the patterned development, the substrate A was immersed in the liquid for immersion exposure shown in Table 11 for 30 seconds, and then PEB, development and rinsing were performed in the same manner as above to obtain the substrate B after development. After development, the board | substrate A and B were observed with the scanning electron microscope (made by Hitachi Keisukuki Co., Ltd.) S-9360, and the pattern corresponding to the mask pattern of a 90 nm line and a 90 nm space. At this time, "(circle)" and the case where a favorable spherical resist pattern of the same shape are obtained with respect to the board | substrate A and B after visual development are obtained as "x". "-" Indicates not to evaluate.

Patterning Assessment Exam (2)

The wafer subjected to exposure under the same conditions as in the patterning evaluation test (1) was immersed in the liquid for immersion exposure for 30 seconds, and then subjected to PEB, development and rinsing in the same manner as above to obtain a substrate C after development. At this time, the case where a good spherical resist pattern of the same shape is obtained with respect to the substrates A and C with the naked eye is set to "x" and the case where the same shape pattern is not obtained is "x". "-" Indicates not to evaluate.

(4) contact angle measurement experiment

Measurement of the contact angle of trans-decalin to the resist films H2, H4, H5 and quartz glass was carried out using Crude, mode IDSA10L2E (Measurement Ellipse (tangent 1) method). The results are shown in Table 12.

(5) Exposure experiment using two beam interference

The evaluation resist film prepared by the same method as the resist film H2 was applied, except that the film thickness of the lower layer antireflection film was set to 29 nm and the resist film thickness was set to 100 mm (for 45 nm) -60 mm (for 35 nm). About the wafer, between a lens and a wafer of the simple exposure apparatus for 2-beam interference type ArF immersion (for 45 nm 1L / 1S by Canon, the Nikon Corporation make, 35 nm 1L / 1S, using TE polarized light exposure) 0.7 mm) and then exposing the liquid for immersion exposure after purification to expose the liquid. Then, the liquid immersion exposure liquid on the wafer is removed by air drying, and the wafer is PEB (115 ° C, 90) with a clean track act 8 hot plate. Second), puddle development (developer component, 2.38 wt% tetrahydroammonium hydroxide aqueous solution) (for 60 seconds) with the LD nozzle of the same clean track Act 8, and rinse with ultrapure water to develop the substrate after scanning using a scanning electron microscope (Manufactured by Hitachi Keisukuki Co., Ltd.) S-93 The pattern was observed at 60. At this time, "(circle)" and the case where a good pattern is not obtained are set to "x" for the case where the resist pattern with favorable L / S (1L / 1S) of a desired dimension is obtained. The results are shown in Table 13.

(6) absorbance change (or contamination) upon resist contact

A liquid (deionized water or trans-decalin (2) (another lot product purified in the same manner as in Example 2) after purification) was added to a 6 cm diameter chalet using a glass pipette at which the film thickness of the liquid was The liquid amount was adjusted to 1 mm, and then the upper part of the chalet was covered with a silicon wafer coated with photoresist H1 and H4, and then the upper and lower sides of the wafer and the chalet were reversed, so that a liquid was immersed in the photoresist film. At this time, the wafer is firmly adhered so that there is no leakage of liquid from between the chalet and the wafer, and care is taken so that the wafer is horizontal so that the photoresist is uniformly immersed in the liquid in all parts covered with the chalet. The upper and lower sides of the wafer and the chalet were reversed again, and after a series of these operations, the liquid was collected to measure the absorbance at 193.4 nm. Example B performed by the method, the measured value was calculated based on the absorbance per 1 ㎝ absorbance. In addition, the series of operations which were carried out in a glove box filled with nitrogen at 23 ℃. The results are shown in Table 14.

As shown in Table 11, since the liquid for liquid immersion exposure of the present invention has a refractive index larger than that of pure water and has a chemical structure represented by Chemical Formulas 1-1 to 1-9, it exhibits excellent resolution and at the same time forms a resist film alone or an upper layer film. The resist film is not dissolved, the film component is not eluted, or the resulting resist pattern shape is not deformed. In addition, as shown in Table 14, it was found that decalin after purification had no change in absorbance after extraction for 180 seconds of dipping time.

In addition, as a method for evaluating the liquid for immersion exposure, the liquid immersion exposure liquid is brought into contact with a liquid immersion exposure liquid and a photoresist film formed on the substrate, and the absorbance change at 193 nm of the liquid before and after contact is measured and compared to thereby contaminate the liquid immersion exposure liquid. We can see that we can evaluate.

Since the liquid for liquid immersion exposure of the present invention is a cyclic hydrocarbon compound containing an alicyclic hydrocarbon compound or a silicon atom in a ring structure, it is possible to form a resist pattern excellent in resolution and developability without dissolving a photoresist film during liquid immersion exposure. It can be used in the manufacture of a semiconductor device which is expected to further refine the future in the future.

Claims (24)

A liquid used in an immersion exposure apparatus or an immersion exposure method for exposing through a liquid filled between a lens of a projection optical system and a substrate, wherein the liquid is a liquid in a temperature range in which the immersion exposure apparatus operates, and an alicyclic hydrocarbon compound or silicon It is a liquid containing the cyclic hydrocarbon compound which contains an atom in a ring structure, and the cyclic hydrocarbon compound which contains the said alicyclic hydrocarbon compound or a silicon atom in a ring structure has 70% of the radiation transmittance per 1 mm of optical path lengths in wavelength 193nm. The refractive index of the D line is 1.4 or more, wherein the liquid for liquid immersion exposure is described above. The liquid immersion exposure liquid according to claim 1, wherein the cyclic hydrocarbon compound containing the alicyclic hydrocarbon compound or the silicon atom in the ring structure is a compound of one garment selected from the following Chemical Formulas 1-1 to 1-9. <Formula 1-1>

In Formula 1-1, R ¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom, or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and n1 and n2 each independently An integer of 1 to 3 is represented, a represents an integer of 0 to 10, and when a plurality of R ¹ are present, these R ¹ may be the same or different, and two or more R ¹ are bonded to each other to form a ring structure You may.) <Formula 1-2>

In Formula 1-2, A represents a methylene group which may be substituted with a single bond or an alkyl group having 1 to 10 carbon atoms or an alkylene group having 2 to 14 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms, and R ² is An aliphatic hydrocarbon group of 1 to 10 carbon atoms, an alicyclic hydrocarbon group of 3 to 14 carbon atoms, a fluorine atom or a fluorine-substituted hydrocarbon group of 1 to 3 carbon atoms, R ⁷ represents a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, a fluorine atom or carbon number When a fluorine substituted alkyl group of 1 to 3 is present and a plurality of R ^{7 's} are present, these R ^{7' s} may be the same or different, two or more R ^{7 's} may be bonded to each other to form a ring structure, and n 3 may be 2 to 3 An integer of 4 is represented, n4 represents an integer of 1 to 3, b represents an integer of 0 to 6, and when a plurality of R ² are present, these R ² may be the same or different and two or more; R ² on the phase may combine with each other to form a ring structure.) <Formula 1-3>

In Formula 1-3, R ³ and R ⁴ represent an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom, or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and R ³ and R ^{When a} plurality of ⁴ 's each exist, these R ³ and R ⁴ may be the same or different, respectively, two or more R ³ and R ⁴ may be each alone or combine with each other to form a ring structure, n5 and n6 Represents an integer of 1 to 3, and c and d represent an integer of 0 to 8.) <Formula 1-4>

(In (a), (b), (c) in Formula 1-4, B represents a methylene group or an ethylene group, R ⁵ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an alicyclic hydrocarbon group having 3 to 14 carbon atoms). , A fluorine atom or a C1-C3 fluorine-substituted hydrocarbon group, e represents an integer of 0 to 10, n7 represents an integer of 1 to 3, and when a plurality of R ⁵ are present, these R ⁵ are the same or It may be different, or two or more R ⁵ may combine with each other to form a ring structure.) <Formula 1-5>

In Formula 1-5, R <^6> represents a C1-C10 aliphatic hydrocarbon group, a C3-C14 alicyclic hydrocarbon group, a fluorine atom, or a C1-C3 fluorine-substituted hydrocarbon group, f is an integer of 0-10. In the case where a plurality of R ^{6 's} are present, these R ^{6' s} may be the same or different.) <Formula 1-6>

In Formula 1-6, R ⁸ And R ^{8 '} represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and g and h each represent an integer of 0 to 6; , n8 and n9 represent integers of 1 to 3.) <Formula 1-7>

In Formula 1-7, R ¹¹ And R ¹² represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and n10 and n11 each independently represent an integer of 1 to 3; J, k represent an integer of 0 to 6, and R ¹¹ And when there are a plurality of R ¹² 's respectively, these R ¹¹ and R ¹² may be the same or different, two or more R ^{11' s} may combine with each other to form a ring structure, or two or more R ^{12 's} may be bonded to each other To form a ring structure, X represents a single bond, a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms, and a divalent alicyclic hydrocarbon group having 3 to 14 carbon atoms.) <French 1-8>

In formula (1-8), R ¹³ represents an alkyl group having 2 or more carbon atoms, an alicyclic hydrocarbon group having 3 or more carbon atoms, a fluorine atom or a fluorine substituted hydrocarbon group having 2 to 3 carbon atoms, p represents an integer of 1 to 6, and R ¹³ is When two or more exist, these R <^13> may be same or different and two or more R <^13> may combine with each other, and may form ring structure.) <Formula 1-9>

In Formula 1-9, R ¹⁴ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom, or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and n12 is an integer of 1 to 3 Q represents an integer of 0 to 9, and when a plurality of R ^{14 's} are present, these R ¹⁴ may be the same or different.) The liquid according to claim 2, wherein the compound represented by Chemical Formula 1-1 is represented by the following Chemical Formula 2-1, and the compound represented by Chemical Formula 1-4 is represented by the following Chemical Formula 2-2. . <Formula 2-1>

<Formula 2-2>

In Formula 2-1, R ¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom, or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and a represents an integer of 0 to 10. represents, when a plurality of R ¹ are present, these R ¹ are the same or different, two or more R ¹ may combine with each other to form a cyclic structure, In Formula 2-2, R ⁵ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom, or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and i represents an integer of 0 to 2. represents, when a plurality of R ⁵ is present, these R ⁵ are the same or may be different, two or more of R ⁵ to form a ring structure by bonding with each other. 2. The change in absorbance per cm of optical path length of 193 nm of the liquid before and after the contact is 0.05 when the liquid is brought into contact with the liquid film with a thickness of 1 mm for 180 seconds in a nitrogen atmosphere. Liquid for liquid immersion exposure, characterized by the following. The liquid immersion exposure liquid according to claim 1, wherein the cyclic hydrocarbon compound containing the alicyclic hydrocarbon compound or the silicon atom in the ring structure is contained in an amount of 95% by weight or more based on the whole liquid for liquid immersion exposure. The liquid for liquid immersion exposure according to claim 1, wherein the dissolved oxygen amount of the liquid is 2 ppm or less. The liquid for liquid immersion exposure according to claim 1, wherein the total amount of the metal containing the liquid is 10 ppb or less. The liquid for liquid immersion exposure according to claim 7, wherein the metal is at least one metal selected from lithium, sodium, potassium, magnesium, copper, calcium, aluminum, iron, zinc and nickel. The liquid for liquid immersion exposure according to Claim 1, wherein the liquid has a viscosity at 25 ° C. of 0.01 Pa · s or less. The liquid for liquid immersion exposure according to claim 1, wherein the refractive index at a wavelength of 193 nm is 1.63 or more. The liquid immersion exposure liquid according to claim 10, wherein a radiation transmittance per 1 mm of optical path length at a wavelength of 193 nm is 95% or more. The compound represented by the formula (2-1) is trans-decahydronaphthalene, the radiation transmittance per 1 mm of optical path length at a wavelength of 193 nm is 95% or more, and the amount of dissolved oxygen is 2 ppm or less. Liquid for liquid immersion exposure. The liquid for liquid immersion exposure according to claim 12, wherein the trans-decahydronaphthalene raw material is a liquid having a purity of 95 wt% or more obtained by washing and distilling concentrated sulfuric acid under a nitrogen atmosphere. The compound represented by the formula (2-2) is exo-tetrahydrodicyclopentadiene, the radiation transmittance per 1 mm of optical path length at a wavelength of 193 nm is 95% or more, and the amount of dissolved oxygen is 2 ppm or less. A liquid for liquid immersion exposure, characterized in that. The liquid for liquid immersion exposure according to claim 14, wherein the exo-tetrahydrodicyclopentadiene raw material is a liquid having a purity of 95% by weight or more obtained by washing and distilling concentrated sulfuric acid under a nitrogen atmosphere. The liquid immersion of Claim 1 provided with the liquid containing the cyclic hydrocarbon compound which contains an alicyclic hydrocarbon compound or a silicon atom in a ring structure under nitrogen atmosphere, at least 1 step of a concentrated sulfuric acid washing process and a distillation process. The manufacturing method of the liquid for exposure. A liquid immersion exposure method for illuminating a mask with an exposure beam and exposing the substrate with the exposure beam through a liquid filled between the lens of the projection optical system and the substrate, wherein the liquid is a liquid for liquid immersion exposure according to claim 1 Immersion exposure method. 18. The liquid according to claim 17, wherein an upper layer film for immersion is formed on a surface of the resist film on the substrate, and the upper layer film for immersion is soluble in an alkaline developer and contains a resin component insoluble in the liquid for exposure immersion according to claim 1. An immersion upper layer film, and having a hexafluorocarbinol group and at least one group of a carboxyl group as a substituent for imparting alkali solubility. It is a contamination degree evaluation method for evaluating the contamination degree at the time of using the liquid immersion exposure of the liquid used for the liquid immersion exposure apparatus or liquid immersion exposure method which exposes through the liquid filled between the lens of a projection optical system, and a board | substrate, The degree of contamination of the liquid for immersion exposure is evaluated by contacting the liquid for immersion exposure and the photoresist film formed on the substrate under nitrogen atmosphere, and measuring and comparing the change in absorbance at a wavelength of 193 nm of the liquid before and after contact. Method for evaluating contamination of liquid for exposure. 95 wt% or more of the compound represented by the following Chemical Formula 2-1 or the following Chemical Formula 2-2 is contained, and the amount of dissolved oxygen is 2 ppm or more. <Formula 2-1>

<Formula 2-2>

In Formula 2-1, R ¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom, or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and a represents an integer of 0 to 10. represents, when a plurality of R ¹ are present, these R ¹ are the same or different, two or more R ¹ may combine with each other to form a cyclic structure, In formula (2-2), R ⁵ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, a fluorine atom, or a fluorine substituted hydrocarbon group having 1 to 3 carbon atoms, and i represents 0 to 2 when an integer, R ⁵ is a plurality is present, these R ⁵ are the same or may be different, two or more of R ⁵ to form a ring structure by bonding with each other. The liquid immersion exposure liquid composition according to claim 20, wherein the total amount of the metals contained in the liquid composition is 10 ppb or less. 21. The liquid immersion exposure liquid composition according to claim 20, wherein the compound represented by Chemical Formula 2-1 is trans-decahydronaphthalene, and the radiation transmittance per mm of the optical path length at a wavelength of 193 nm is 95% or more. The liquid immersion lithography liquid composition according to claim 20, wherein the compound represented by Chemical Formula 2-2 is exo-tetrahydrodicyclopentadiene, and has a transmittance of 95% or more per 1 mm of optical path length at a wavelength of 193 nm. . The liquid immersion exposure liquid composition according to claim 20, wherein the compound represented by Chemical Formula 2-1 or 2-2 is purified by one or more methods of concentrated sulfuric acid washing and distillation under a nitrogen atmosphere.